Pigment dispersion

ABSTRACT

Fluid concentrates, colorants and coating compositions contain solid pigment particles dispersed in a nonvolatilizing, reactive liquid diluent having a viscosity less than 1,000 cps and containing at least one molecular species having at least three reactive unsaturated sites. The reactive liquid diluent may serve as one or more of a dispersing medium for the solid pigment particles, a carrier, a coalescent and a humectant, and may crosslink or otherwise cure to form an interpenetrating polymer network in, or crosslink with, a pigmented coating composition containing a film-forming polymeric binder. Embodiments of the reactive liquid diluent can provide colorants and coating compositions having reduced levels of VOCs, conventional carriers, conventional dispersants, conventional coalescents and conventional humectants.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. application Ser. No.15/563,133 filed on Sep. 29, 2017, now patented U.S. Pat. No. 10,836,910and entitled “PIGMENT DISPERSION,” which is the §371 U.S. National Stageof International Application No. PCT/US2016/025752 filed on Apr. 1, 2016and entitled “PIGMENT DISPERSION,” which claims the benefit of U.S.Provisional Application Ser. No. 62/141,710 filed on Apr. 1, 2015 andentitled “REACTIVE PIGMENT DISPERSION,”the disclosures of which areincorporated herein by reference in their entireties.

FIELD

This invention relates to pigment dispersions for use in colorants usedin tinting paints, stains and other coating compositions.

BACKGROUND

Paints, stains and other protective, decorative or functional coloredfluid coatings may be supplied in a small number of popular premixed,pretinted colors. A line of such coatings may be manufactured in afactory by combining selected powdered pigments with appropriatesolvents or other liquid carrier(s), pigment wetting or dispersingagents, fluid coating binders and other coating composition adjuvants,and properly mixing the ingredients to provide a storage-stablepremixed, pretinted coating composition.

In order to accommodate end user desires and to enable the matching ofcolors on existing coated surfaces, coating manufacturers may also orinstead distribute a set of tintable base coatings (e.g., base paints)and an array of concentrated point-of sale fluid colorants viapoint-of-sale outlets (e.g., retail paint stores, mobile retailvehicles, hardware stores, building supply stores, warehouses anddistribution centers). After consulting color charts, color chips, colordisplays, or an appropriate color measurement or color matching system,selected amounts of one or more fluid colorants are metered, usingmanual or automated colorant dispensing equipment located at thepoint-of-sale outlet, into a can or other container nearly filled withthe base coating composition, and then mixed using a paint shaker orother mixing device. This approach can provide small batch lots ofcustom-tinted paint in a much larger array of colors than the limitedcolors available in premixed pretinted products. Alternatively, acontainer can be filled with the base coating composition and one ormore fluid colorants at the point-of-sale outlet and mixed either duringor after the filling operation.

Whether manufacturing a premixed pretinted coating composition or thecolorant for use in a point-of sale custom tint system, themanufacturing process typically requires wetting a mass of dry powderedpigment particles and converting the wetted mass into a highly-loadeddispersion using suitable mixing equipment and a liquid carrier. Manypigments require the use of a wetting agent. Depending on the chosenpigment, one or more dispersing agents typically will also be employedto promote particle dispersion and separation, discourage particleagglomeration, and reduce the time required to mix the pigment orcolorant with the base coating composition. Colorants may also containother adjuvants including inert (viz., extender) pigments such as talcor kaolin clay, thickeners such as hydroxyethylcellulose to controlviscosity, humectants such as polyalkylene glycols to discouragedispenser tip drying, and mildewcides or biocides to discouragemicrobial growth.

Many previously-used colorant adjuvants are no longer employed, or areused in reduced amounts, as they release Volatile Organic Compounds(VOCs) and in some instances Hazardous Air Pollutants (HAPs) into theatmosphere. Various National and State regulations limit overall VOC andHAP content, see for example 40 C.F.R. Part 59, National VolatileOrganic Compound Emission Standards for Architectural Coatings.Considerable current research has been directed to finding new pigmentwetting and dispersing agents that will work well with a limited set ofacceptable carriers, and to finding lower-VOC versions of other coatingsystem adjuvants so as not to contribute additional VOC emissions in thefinished coating product. In addition, some volatile nonaqueous carriersmay raise overall VOC emissions from a coating composition either duringor after cure. Less volatile carriers may serve as plasticizers in thefinished coating and thereby contribute to other finished coatingproblems including coating softness, water sensitivity, poor adhesion,or disruption in coating integrity.

From the foregoing, it will be appreciated that what remains needed inthe art are improved systems for dispersing pigments into colorants andinto finished coating compositions without causing undesirable finishedfilm properties. Such systems, colorants, coating compositions andmethods for their manufacture are disclosed and claimed herein.

SUMMARY OF THE INVENTION

The invention provides, in one aspect, a concentrate for use in themanufacture of fluid colorants or finished coating compositions (e.g.,paints), wherein at least 95 wt. % of the concentrate is a mixture of(i) solid pigment particles with (ii) a nonvolatilizing, reactive liquiddiluent having a viscosity less than 1,000 cps and containing at leastone molecular species having at least three reactive unsaturated sites,wherein when the reactive liquid diluent does not by itself stablydisperse the pigment particles then the concentrate also contains (iii)one or more pigment wetting or dispersing agents. The disclosedconcentrates contain less than 5 wt. % of materials other than thepigment particles, reactive liquid diluent and pigment wetting ordispersing agents, and in some embodiments may consist of or consistessentially of the pigment particles, reactive liquid diluent and (ifneeded) the pigment wetting or dispersing agents. The concentrateaccordingly contains less than 5 wt. % of film-forming polymeric bindersand more preferably does not contain film-forming polymeric binders. Ina factory setting, the disclosed concentrates may be diluted or “letdown” with additional wetting aids or dispersing agents and with othercolorant ingredients (e.g., pigments, volatile or non-volatile carriersand other colorant adjuvants) to form an array of point-of-sale fluidcolorants. The disclosed concentrates may also be let down with wettingaids or dispersing agents, other colorant ingredients, and furthercoating composition adjuvants such as film-forming polymeric coatingbinders, volatile carriers and other coating composition adjuvants toform premixed pre-tinted finished coating compositions. The concentratesthus provide useful factory intermediates that simplify manufacturingprocedures and reduce required inventories of raw materials andsemi-finished goods.

The invention provides, in another aspect, a fluid colorant for tintingan unpigmented or pigmented coating composition, the colorant containingless than a continuous film-forming amount of a film-forming polymericbinder, and the colorant comprising: (i) solid pigment particlesdispersed in (ii) a nonvolatilizing, reactive liquid diluent having aviscosity less than 1,000 cps and containing at least one molecularspecies having at least three reactive unsaturated sites, wherein whenthe reactive liquid diluent does not by itself stably disperse thepigment particles then the colorant also contains (iii) one or morepigment wetting or dispersing agents. The disclosed colorant may consistof or consist essentially of the pigment particles, reactive liquiddiluent and (if needed) the pigment wetting or dispersing agents, or mayinclude one or more adjuvants used in colorants or in coating systems.The colorant preferably is substantially free of film-forming polymericbinders and more preferably does not contain film-forming polymericbinders. The colorant may be used for tinting paints, stains and othercoating compositions in a point-of-sale outlet, or for in-plant tintingof paints, stains and other coating compositions in a factory setting.

The invention provides, in another aspect, a colored latex coatingcomposition comprising a film-forming latex polymer binder, solidpigment particles, and a nonvolatilizing, reactive liquid diluent havinga viscosity less than 1,000 cps and containing at least one molecularspecies having at least three reactive unsaturated sites, at least onemolecular species in the reactive liquid diluent containing at least onereactive unsaturated site as well as at least one hydrophilic segmentthat enables such species to stably disperse the pigment particles inthe coating composition. The disclosed latex coating composition maydry, cure or otherwise harden by a variety of mechanisms including oneand preferably more than one of binder film coalescence and loss of avolatile carrier; radiation curing such as UV-, visible light or e-beamradiation; thermal crosslinking; chemical crosslinking; or via theoperation of a catalytic component, for example a metal drier, that cancatalyze reaction (e.g., chain extension or crosslinking) ofunsaturation in the reactive liquid diluent or binder.

The invention provides, in another aspect, a method for making a factoryintermediate concentrate, the method comprising dispersing solid pigmentparticles into a nonvolatilizing, reactive liquid diluent having aviscosity less than 1,000 cps and containing at least one molecularspecies having at least three reactive unsaturated sites, wherein whenthe reactive liquid diluent does not by itself stably disperse thepigment particles then the particles are dispersed in the presence ofone or more pigment wetting or dispersing agents, the method forming aconcentrate at least 95 wt. % of which is a mixture of the pigmentparticles, reactive liquid diluent and (if needed) the pigment wettingor dispersing agents, the concentrate being useful as a factoryintermediate for making point-of-sale fluid colorants or premixedpretinted finished coating compositions. The concentrates made by suchmethod contain less than 5 wt. % of materials other than the pigmentparticles, reactive liquid diluent and pigment wetting or dispersingagents, and in some embodiments may consist of or consist essentially ofthe pigment particles, reactive liquid diluent and (if needed) thepigment wetting or dispersing agents. Preferably in such method theconcentrate is substantially free of film-forming polymeric binders andmore preferably the concentrate does not contain film-forming polymericbinders.

The invention provides, in a further aspect, a method for makingpoint-of-sale fluid colorants, the method comprising: dispersing solidpigment particles into a nonvolatilizing, reactive liquid diluent havinga viscosity less than 1,000 cps and containing at least one molecularspecies having at least three reactive unsaturated sites, wherein whenthe reactive liquid diluent does not by itself stably disperse thepigment particles then the particles are dispersed in the presence ofone or more pigment wetting or dispersing agents, the colorantcontaining less than a continuous film-forming amount of a film-formingpolymeric binder. Preferably in such method the colorant issubstantially free of film-forming polymeric binders and more preferablythe colorant does not contain film-forming polymeric binders.

The present invention provides, in yet another aspect, a method formaking colored fluid latex coating compositions, the method comprisingforming in one or more mixing steps a dispersion containing (i) solidpigment particles, (ii) a film-forming latex polymer binder, (iii) anonvolatilizing, reactive liquid diluent having a viscosity less than1,000 cps and containing at least one molecular species having at leastthree reactive unsaturated sites, at least one molecular species in thereactive liquid diluent containing at least one reactive unsaturatedsite as well as at least one hydrophilic segment that enables suchspecies to stably disperse the pigment particles in the coatingcomposition, (iv) an optional volatile carrier, (v) a metal drier orother free radical polymerization catalyst and (vi) coating compositionadjuvants.

The disclosed concentrates, fluid colorants, fluid coating compositionsand methods may obviate the need to use other normally requiredingredients in colorants and coating compositions, and can providecolorants and colored coating compositions having very low VOC levels aswell as other highly desirable property improvements.

Definitions

The recitation of a numerical range using endpoints includes all numberssubsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, 5, etc.).

The terms “a,” “an,” “the,” “at least one,” and “one or more” are usedinterchangeably. Thus, for example, a coating composition that contains“an” additive means that the coating composition includes “one or more”additives.

The term “automated colorant dispenser” means a dispenser that iscontrolled or controllable via electronically-regulated precision pumpsor other electronically-regulated fluid flow management devices so as tometer quantities of one or more fluid colorants into a container for acoating composition and thereby facilitate preparation of tinted coatingcompositions whose tints are selected from an array of tints. A manualcolorant dispenser typically lacks such pumps or other fluid flowmanagement devices, and typically uses a hand-operated piston todispense and meter colorant. For either automated or manual colorantdispensers, the container into which colorant is metered may alreadycontain a base coating composition at the time of colorant addition, orthe base coating composition and colorants may be added to the containerconcurrently or sequentially in any order.

The term “binder” means a natural or synthetic polymer suitable for usein paints and other coating compositions to form pigment-containingdried, cured or otherwise hardened coatings in which the binder mayrepresent a continuous phase.

The term “carrier” means a volatile aqueous or organic liquid solvent ordispersant that can be used to prepare paints and other coatingcompositions containing suspended pigments and other suspended solidparticulate materials.

The terms “color” and “colored” when used with respect to a colorant ora coating composition include not only primary hues (for example, thered, yellow and blue principal hues in the RYB color system, or the red,yellow, green, blue and purple principal hues in the Munsell colorsystem), but also intermediate-hued, black-hued and white-hued colorantsand coating compositions.

The term “color strength” refers to the value obtained using DatacolorTOOLS™ software and a Datacolor SPECTRAFLASH™ SF300 or similarspectrophotometer to measure the color strength of a paint sampleapplied using a 4 mil (0.1 mm) BIRD™ bar applicator to a BYK-GARDNER™plain white chart, and using a D65 illuminant, CIE 1964 10° StandardObserver angle and reflectance mode.

The term “colorant” refers to a composition that may be added to a basecoating composition (e.g., a base paint or stain) so as to alter the hueor lightness of such base coating composition, and which typically andpreferably is substantially free of high molecular weight film-formingpolymeric binders like those normally used in paints and other coatingcompositions.

The term “colorant array” refers to a collection of compatible colorantsin a variety of hues including at least one white colorant, blackcolorant, yellow-hued colorant, green-hued colorant, blue-hued colorantand red-hued colorant, the colorants in such array having relatedpackaging and Stock Keeping Unit (“SKU”) identification and beingdesigned to be combined, typically using a point-of-sale automated ormanual colorant dispenser, with one or more compatible base coatingcompositions to provide an array of custom tints selectable by apainting contractor, consumer or other end user.

The term “concentrate” means a composition that may be used in a factoryas an intermediate from which is made fluid colorants for use inpoint-of-sale dispensing equipment, or from which is made premixedpre-tinted fluid coating compositions, and which contains the disclosedsolid pigment particles, the disclosed reactive liquid diluent and ifneeded pigment wetting or dispersing agent.

The term “crosslinking molecule” when used with respect to a molecularspecies in the disclosed reactive liquid diluent means a nonvolatilizingmolecular species that is a liquid at room temperature and containsreactive sites capable of IPN formation in a fluid pigmented coatingcomposition containing a film-forming polymeric binder and a volatilecarrier, or capable of crosslinking such binder, but which molecularspecies does not by itself serve as a pigment dispersing agent thatenables formation of a stable dispersion of 25 wt. % of such pigment in50 wt. % of such carrier.

The term “custom-tinted” when used with respect to a system or methodfor tinting base coating compositions means that one or more colorantscan be dispensed into the base coating composition and mixed to providefinished coating compositions in a wide variety of (e.g., more than 20,more than 100 or even more than 1,000) preselected formulated colors or,if desired, so dispensed and mixed to match a preexisting color.

The term “dispersion” when used with respect to a fluid concentrate,colorant or coating composition means that the concentrate, colorant orcoating composition contains particles uniformly distributed in acontinuous liquid phase.

The terms “extender particle” and “extender pigment” mean a particulatesolid material that does not materially affect tint but can be includedin a paint or other coating composition to reduce the amount of colored(viz., prime) pigment required to attain a desired tint or colorstrength, or for affecting other properties such as oil absorption,flatness, opacity, film strength, film hardness, corrosion resistance,film permeability or coating composition viscosity.

The term “film-forming” when used in reference to a polymeric bindermeans that a solution or dispersion of the polymeric binder can becoated in a thin wet layer (e.g., of about 150-200 μm thickness) on asuitable support, and dried, cured or otherwise hardened (if need bewith the aid of a suitable coalescent) to form over the support asubstantially continuous dry film coating layer (e.g., of about 75-100μm thickness) containing the polymer.

The terms “fluid” and “liquid” when used in reference to a substancemean that the substance is readily flowable at room temperature (e.g.,20° C.) and with minimal or modest shear over a time period of about oneminute. A fluid may also contain dispersed solid particles.

The terms “latex polymer” or “emulsion polymer” when used with respectto a waterborne particulate polymer mean the polymer is not itselfcapable of being dispersed into water; rather, a latex or emulsionpolymer requires the presence of a secondary emulsifying agent (e.g., asurfactant, and typically present during latex polymerization) to createan emulsion of the polymer particles in water.

The terms “low temperature coalescence” and “LTC” when used in referenceto a fluid coating composition containing a film-forming polymeric latexbinder refer to the comparative coalescence of a series of latex paintsas measured for example using ASTM D3793-06. This ASTM standard was notupdated within the time period required by ASTM regulations and thus waswithdrawn in 2012. The standard may exhibit some variability betweenresults measured in different laboratories, but may nonetheless be usedto compare coalescence results obtained within a single laboratory.

The term “low viscosity” means having a viscosity less than 1,000centipoise (cps). Unless otherwise specified herein, viscosity isevaluated using a BROOKFIELD™ rotational viscometer with a No. 2 spindleat 20 rpm and 25° C.

The term “low VOC” when used with respect to colorants, paints and othercoating compositions means that the colorant or coating compositioncontains less than about 50 g/L volatile organic compounds. VOC levelsmay be measured using ASTM D6886-14 with methyl palmitate as the boilingpoint marker.

The term “(meth)” when used as a prefix for the term “allyl” refers toboth methallyl and allyl groups, and when used as a prefix for the term“acrylate” refers to both methacrylate and acrylate groups.

The term “monomer” means a reactive organic molecule that can bondcovalently to other molecules or to itself to form an oligomer or apolymer containing a plurality of units (e.g., a plurality of repeatingunits) derived from the monomer.

The term “nonreactive” when used with respect to a carrier or otheringredient in a colorant or coating composition means that the carrieror other ingredient does not bond (e.g., covalently) with itself or withother ingredients in such colorant or coating composition during storagethereof, and in some embodiments also does not bond during drying, cureor other hardening thereof. Some ingredients (for examplethermally-activated blocking agents) may be nonreactive during storageof a colorant or coating composition and become reactive during drying,cure or hardening.

The term “nonvolatilizing” when used with respect to a molecular speciesor other material means that it is less volatile than methyl palmitatewhen evaluated using ASTM D6886-14.

The term “oligomer” means a molecule of intermediate relative molecularmass, the structure of which essentially contains a small plurality ofunits derived, actually or conceptually, from molecules of lowerrelative molecular mass, and having properties that vary significantlywith the removal of one or a few of the units.

The term “opaque” when used with respect to paints and other coatingcompositions means that the coating composition has a contrast ratiogreater than 95% at a 100 μm (4 mil) dry film thickness. The contrastratio may be determined by dividing the L* value measured over the blackportion of a BYK-Gardner opacity drawdown chart by the L* value measuredover the white portion.

The term “pigment” means a natural or synthetic particulate materialhaving light-reflective or light-absorptive characteristics and asurface energy and particle size suitable for use in coloring paints andother coating compositions, and will be construed to include bothinsoluble materials such as inorganic or organic powdered pigments, andsoluble materials such as organic dyes.

The terms “pigment volume concentration” or “PVC” when used with respectto a coating composition containing pigment particles, the disclosedreactive liquid diluent and a film-forming polymeric binder mean thetotal percentage of the dried solids occupied by a recited pigmentspecies (or if no pigment species is recited, then by all pigmentspecies) in a cured mixture made from the film-forming polymeric binder,pigment particles, extender particles and other coating compositionadjuvants in a comparison coating composition made without including thedisclosed reactive liquid diluent in such mixture. The terms “criticalpigment volume concentration” or “CPVC”, refer to the PVC level at whichthere is just enough of the film-forming polymeric binder to wet all theavailable pigment particle surfaces. The pigment particles willaccordingly be entirely surrounded by binder below the CPVC, and willnot be so surrounded above the CPVC. Above CPVC, a comparison coatingcomposition made by mixing the binder with the pigment particles,extender particles and other coating composition adjuvants but withoutincluding the disclosed reactive liquid diluent in such mixture, willform a discontinuous rather than a continuous film.

The term “point-of-sale” means a site at which custom-mixed coatingcompositions are tinted and mixed in small batch lots (e.g., one halfpint, one pint, one quart, one liter, one gallon, four liter, fivegallon or 20 liter containers, corresponding to containers from about0.2 to 20 L) for sale to end users (e.g., painters, builders andhomeowners). Representative point-of-sale outlets include retail paintstores, mobile retail vehicles, hardware stores, building supply stores(including warehouses), and distribution centers.

The terms “polymer” and “polymeric” include polymers as well ascopolymers of two or more monomers, and refer to a molecule of highrelative molecular mass, the structure of which essentially contains themultiple repetition of units derived, actually or conceptually, frommolecules of low relative molecular mass, and having properties that donot vary significantly with the removal of one or a few of the unitsfrom such polymer.

The terms “preferred” and “preferably” refer to embodiments of theinvention that may afford certain benefits, under certain circumstances.However, other embodiments may also be preferred, under the same orother circumstances. Furthermore, the recitation of one or morepreferred embodiments does not imply that other embodiments are notuseful, and is not intended to exclude other embodiments from the scopeof the invention.

The term “reactive” when used with respect to an ingredient in acolorant or coating composition means that such ingredient bonds (e.g.,covalently) with itself or with other ingredients in such colorant orcoating composition (e.g., during drying, cure or other hardeningthereof).

The term “scaffold molecule” when used with respect to a molecularspecies in the disclosed reactive liquid diluent means a nonvolatilizingmolecular species that is a liquid at room temperature, or a solid thatwhen mixed with a crosslinking molecule or crosslinking molecules ofsuch reactive liquid diluent provides a liquid mixture having aviscosity less than 1,000 cps; contains hydrophilic segments andhydrophobic segments and at least one reactive unsaturated site; and ina fluid pigmented coating composition containing a film-formingpolymeric binder and a volatile carrier will serve as a pigmentdispersing agent that enables formation of a stable dispersion of 25 wt.% of such pigment in 50 wt. % of such carrier. A scaffold molecule thatincludes at least two reactive unsaturated sites may also participate incrosslinking a polymeric film-forming binder, and may be referred to asa “crosslinking scaffold molecule”.

The term “solvent-borne” when used with respect to concentrates,colorants and coating compositions means that the major liquid vehicleor carrier for such colorant, concentrate or coating composition is anonaqueous solvent or mixture of nonaqueous solvents.

The terms “stable dispersion” and “stably disperse” refer to adispersion that does not undergo visibly detectable phase separation ifallowed to stand undisturbed in a clear mixing vessel for at least eighthours.

The term “substantially free of” when used with respect to a componentwhich may be found in a colorant, concentrate or coating composition,means containing less than about 5 wt. % of the component based on thetotal composition weight.

The term “topcoat” refers to a coating composition which when dried orotherwise hardened provides a decorative or protective outermost finishlayer on a coated substrate. By way of further explanation, suchtopcoats may be applied in one or more layers and may be applied to bareor primer-coated substrates.

The term “vinyl” when used with respect to an organic group refers to amoiety having the formula —CH═CH₂.

The term “water-borne” when used with respect to concentrates, colorantsand coating compositions means that the major volatile liquid vehicle orcarrier for such colorant, concentrate or coating composition is water.

The term “water-dispersible” when used with respect to a polymer meansthe polymer is itself capable of being dispersed into water withoutrequiring the use of a separate surfactant, or water can be added to thepolymer, to form a stable dispersion at normal storage temperatures.Water-dispersible polymers may include nonionic or anionic functionalityon the polymer to assist in rendering the polymer water-dispersible. Forsuch polymers, external acids or bases are typically required foranionic stabilization; however, these are not considered to be secondaryemulsifying agents (e.g., surfactants) such as are used to disperse awater insoluble latex polymer into water.

DETAILED DESCRIPTION

A variety of solid pigment particles may be used in the disclosed fluidconcentrates, colorants and coating compositions, and will be familiarto persons having ordinary skill in the art. Exemplary pigment particlesinclude titanium dioxide, black iron oxide, red iron oxide, transparentred oxide, yellow iron oxide, transparent yellow oxide, brown iron oxide(a blend of red and yellow oxide with black), zinc oxide, magnesiumsilicates, calcium carbonate, aluminosilicates, silica and variousclays, carbon black, lampblack, greens such as phthalocyanine green,blues such as phthalocyanine blue, reds (such as naphthol red,quinacridone red, toulidine red and DPP red, also known as PR254),magentas such as quinacridone magenta, violets (such as quinacridoneviolet and carbazole violet), oranges (such as DNA orange and DPPorange), yellows (such as monoazo yellow and bismuth vanadate yellow),umber, complex inorganic color pigments (also known as CICPs), otherpigments such as those listed in U.S. Pat. No. 5,509,960 (Simpson etal.) and U.S. Pat. No. 7,179,531 B2 (Brown et al.),non-infrared-absorbing pigments such as those listed in U.S. Pat. No.8,752,594 B2 (Gebhard et al.), and plastic pigments such as solid beadpigments (e.g., polystyrene or polyvinyl chloride beads) and microspherepigments containing one or more voids and vesiculated polymer particlessuch as those discussed in U.S. Pat. No. 5,510,422 (Blankenship et al.).Representative pigment suppliers include BASF, E. I. duPont de Nemoursand Company, Expancel Inc., Ferro Corporation, Fluoro-Seal Inc., Kronos,Inc., Millennium Specialty Chemicals Inc., Potter Industries Inc.,Shepherd Color Company, Silbrico Corporation, Tomatec America, Inc.,Trelleborg Fillite Inc., Tronox Corporation, 3M, Bunge FertilizantesS.A. and Yianlid Industrial Co., Limited. Mixtures of pigment particlesmay be and often will be employed. The pigment particles may have avariety of shapes and sizes but desirably will scatter or absorb photonshaving wavelengths in the visible spectral region from about 380 nm toabout 700 nm or in the infrared spectral region above the visiblespectral region. Suitable pigment shapes include spherical shapes, suchas a regular sphere, an oblate sphere, a prolate sphere, and anirregular sphere; cubic shapes such as a regular cube and a rhombus;plate-like shapes including a flat plate, a concave plate, and a convexplate; and irregular shapes. Particles having spherical shapes desirablyhave average diameters of about 10 nm to about 1,000 nm, e.g., at leastabout 100 nm or at least about 200 nm, and less than about 500 nm orless than about 300 nm. Particles having non-spherical shapes desirablyhave a maximum diameter of up to about 1 micrometer, e.g., up to about500 nm or up to about 300 nm. The pigment particles may include one ormore coatings, e.g., of silica, alumina, zirconia or combinationsthereof such as a silica coating and an alumina coating.

The amounts of pigment in the disclosed fluid concentrates, colorantsand coating compositions are best expressed by referring to volumepercent pigment rather than weight percent pigment, owing to differencesin density among the various pigments that typically will be employed.The pigment amount typically will also depend on the chosen pigment,owing to differences in particle size and color strength among availablepigments. As a general rule however, a fluid concentrate or colorantwill contain a greater concentration (for example at least twice theconcentration expressed on a volume percent pigment basis) compared tothe highest concentration of such pigment normally present in a finishedcoating composition containing such colorant. In addition, a concentratetypically will contain a greater pigment concentration and a lowerconcentration of water or other nonreactive carrier than thecorresponding fluid colorant. In one preferred embodiment, a set ofconcentrates suitable for making one or more colorant arrays is preparedusing pigment concentrations that are at or above the highest pigmentconcentrations employed for the corresponding pigment-containingcolorants in such colorant arrays. In a further preferred embodiment, aset of concentrates suitable for making one or more colorant arrays isprepared using the highest pigment concentrations that will provide astable concentrate for any chosen pigment. The pigment amounts in thedisclosed fluid concentrates and colorants will to some extent alsodepend upon the other ingredients present and may be empiricallydetermined. Exemplary pigment amounts for concentrates may for exampleat least about 40, at least about 45, or at least about 50 vol. %pigment, and up to about 70, up to about 65, or up to about 60 vol. %pigment. Suitable amounts may readily be empirically determined bypersons having ordinary skill in the art by evaluating time, equipmentand ingredient requirements needed to obtain satisfactory pigmentdispersion from a selected concentrate, using for example the Hegmanfineness of grind procedure described in ASTM D1210-05(2014).

Exemplary pigment amounts for fluid colorants are for example at leastabout 2, at least about 4, at least about 6, at least about 8, at leastabout 10 or at least about 12 vol. % pigment, and up to about 60, up toabout 50, up to about 40, up to about 30, up to about 25 or up to about20 vol. % pigment. By way of example for particular pigments used tomake colorants, the disclosed fluid colorants may include about 15 toabout 40 vol. % pigment for a white pigment based on titanium dioxide,about 15 to about 40 vol. % pigment for a yellow pigment based onorganic yellow PY74, PY83 or PY184, about 4 to about 40 vol. % pigmentfor a green pigment based on phthalo green PG7, about 4 to about 30 vol.% pigment for a blue pigment based on phthalo blue PB15:2, PB15:3 or PB15:4, about 4 to about 60 vol. % pigment for a red pigment based onPR112, PR209 or PR254 and about 4 to about 30 vol. % pigment for amagenta pigment based on PR122. Suitable amounts for colorantscontaining other pigments may readily be empirically determined bypersons having ordinary skill in the art using appropriate drawdowns andif need be color strength measurements using the color strength test andspectrophotometer discussed above.

Exemplary pigment amounts for coating compositions may be lower than theamounts used in colorants, for example at least about 1, at least about2, at least about 4, at least about 6, at least about 8 or at leastabout 10 vol. % pigment, and up to about 40, up to about 30, up to about20, up to about 30, up to about 25 or up to about 20 vol. % pigment.Suitable amounts may readily be empirically determined by persons havingordinary skill in the art using appropriate drawdowns and if need becolor strength measurements using the color strength test andspectrophotometer discussed above.

The disclosed fluid concentrates and colorants include anonvolatilizing, reactive liquid diluent having a viscosity less than1,000 cps and containing at least one molecular species having at leastthree reactive unsaturated sites. For nonvolatilizing reactive liquiddiluents containing more than one molecular species, preferably lessthan 5 wt. % of the molecular species in such reactive liquid diluentare more volatile than methyl palmitate, and more preferably less than 4wt. %, less than 3 wt. %, less than 2 wt. or less than 1 wt. % of themolecular species in such reactive liquid diluent are more volatile thanmethyl palmitate.

The reactive liquid diluent may contain a single molecular species or aplurality of molecular species. The disclosed species each contain atleast one reactive unsaturated site, and at least one molecular speciesin the disclosed reactive liquid diluent contains at least threereactive unsaturated sites. The disclosed reactive liquid diluentaccordingly may contain a single molecular species having at least threereactive unsaturated sites, or may contain a molecular species having atleast three reactive unsaturated sites mixed with one or more additionalmolecular species each containing at least one reactive unsaturatedsite. Preferably the molecular specie(s) having at least three reactiveunsaturated sites represent the majority by weight, and more preferablyat least 60 wt. % or at least 70 wt. %, of the reactive liquid diluent.The disclosed reactive unsaturated sites may for example be provided byallyl groups, methallyl ether groups, vinyl ether groups, acrylategroups, methacrylate groups or conjugated carbon-carbon double bonds.

Preferably a molecular species in the disclosed reactive liquid diluentcontains at least four, at least five or at least six reactiveunsaturated sites. For example, a reactive liquid diluent molecularspecies containing a conjugated carbon-carbon double bond and four allylether groups would be said to have five reactive unsaturated sites, withthe conjugated carbon-carbon double bond being counted as one of thosesites. More than six reactive unsaturated sites may be present ifdesired, but doing so may also cause an undesirable increase inmolecular weight and viscosity, and thus embodiments having less thaneight or less than seven reactive unsaturated sites may be preferred.Also, and without intending to be bound by theory, reactive liquiddiluents containing molecular species with a high equivalent weight perreactive unsaturated site may provide lower hardness films or slowerdevelopment of film hardness. Accordingly, molecular species in thedisclosed reactive liquid diluent preferably have a molar equivalentweight per reactive unsaturated site that is less than 500 g, morepreferably less than 250 g, yet more preferably less than 200 g and mostpreferably less than 150 g.

Preferably one or more molecular species in the disclosed reactiveliquid diluent contain at least one reactive unsaturated site and one ormore hydrophilic segments that enable such molecular species to serve asa pigment wetting or dispersing agent. In some embodiments, suchmolecular species may serve as the only required pigment wetting ordispersing agent needed to disperse solid pigment particles in aconcentrate, colorant or coating composition, and accordingly may enablereplacement of all or most of the conventional pigment wetting ordispersing agents used to make colorants and pigmented coatingcompositions. Such molecular species may also become reacted into acoating composition during the cure thereof and thereby become lesslikely to evolve from the coating and contribute to VOC emissions.

Preferably all the molecular species in the reactive diluent willcrosslink or otherwise become reacted into a coating composition duringthe cure thereof, e.g., by forming or becoming part of aninterpenetrating polymer network (“IPN”) in a hardened film of thecoating composition. In an embodiment, the reactive liquid diluent willalso or instead crosslink with a suitable reactive group on afilm-forming polymeric binder within such coating composition, andthereby become a part of the hardened binder.

Preferably the reactive liquid diluent has a viscosity less than 500cps, less than 300 cps, less than 200 cps or less than 100 cps.Molecular species in the disclosed reactive liquid diluent may have avariety of molecular weights, for example a number average molecularweight of at least about 200, at least about 400, at least about 600 orat least about 800, and up to about 3,000, up to about 2,000, up toabout 1,500 or up to about 1,000.

The disclosed reactive liquid diluent preferably at least partiallyreplaces carriers and other potentially objectionable adjuvants incolorants and coating compositions. The reactive liquid diluentaccordingly may reduce VOC levels prior to or during coating compositioncure, and may reduce coating plasticization after cure. Some embodimentsof the disclosed reactive liquid diluent may serve as the only requiredmedium needed to form a stable dispersion of solid pigment particles,and accordingly may enable replacement of all or most of theconventional carrier or carriers used in some colorants and pigmentedcoating compositions.

An array of fluid colorants containing the disclosed reactive liquiddiluent can enable point-of-sale tinting of base paints and othercoating compositions in a variety of hues. In embodiments in which thereactive liquid diluent is employed in a point-of-sale colorant system,the reactive liquid diluent may also assist in preventing dispenser tipdrying, and accordingly may enable replacement of all or most of theconventional humectants used in such colorant systems.

Some embodiments of the disclosed reactive liquid diluent may assist infilm coalescence by a pigmented latex coating composition, andaccordingly may enable replacement of all or most of the conventionalcoalescents used in some latex coating compositions.

Some molecular species in the disclosed reactive liquid diluents may beclassified as crosslinking molecules, scaffold molecules or ascrosslinking scaffold molecules,

In one preferred subclass representing an embodiment of a crosslinkingmolecule, the reactive liquid diluent may comprise, consist essentiallyof, or consist of a single molecular species having three or more andpreferably four or more reactive unsaturated sites that can react toform the disclosed IPN or can crosslink a film-forming polymeric binderin a coating composition, but which molecular species does not by itselfstably disperse pigment particles. Preferred reactive unsaturated sitesin such single molecular species include (meth)allyl ether groups, vinylether groups and (meth)acrylate groups.

In another preferred subclass representing an embodiment of acrosslinking scaffold molecule, the reactive liquid diluent maycomprise, consist essentially of, or consist of a single molecularspecies having at least three (and preferably at least four) reactiveunsaturated sites that can react to form the disclosed IPN or cancrosslink a film-forming polymeric binder in a coating composition, atleast one hydrophilic segment (e.g., a polyoxyethylene segment) thatenables such molecular species by itself to stably disperse pigmentparticles, and at least one hydrophobic segment, and having a viscosityless than 1000 cps.

In another preferred subclass representing an embodiment of acrosslinking molecule and a separate scaffold molecule, the reactiveliquid diluent may comprise, consist essentially of, or consist of twoor more molecular species each containing one or more reactiveunsaturated sites that can participate in formation of the disclosed IPNor crosslinking of a film-forming polymeric binder, and wherein at leastone molecular species has at least three (and preferably at least four)such reactive unsaturated sites but which molecular species does not byitself stably disperse pigment particles; at least one other molecularspecies contains at least one hydrophilic segment (e.g., apolyoxyethylene segment) that enables such other molecular species byitself to stably disperse pigment particles, and at least onehydrophobic segment; and a mixture of the molecular species in thereactive liquid diluent has a viscosity less than 1000 cps.

A variety of crosslinking molecules and scaffold molecules (includingcrosslinking scaffold molecules) may be used in the disclosed reactiveliquid diluent. The individual molecular species preferably each have amolecular weight that is sufficiently high so that the molecular specieswill be nonvolatilizing, and a molecular weight that is sufficiently lowso that the molecular species will have a viscosity less than 1000 cps.Preferably each such molecular species can serve as a medium in whichpigment particles can be dispersed without requiring the addition of anadditional volatile carrier.

When evaluated by itself, the crosslinking molecule viscosity may forexample be less than 1,000 cps, less than 500 cps, less than 400 cps,less than 300 cps, less than 200 cps or less than 100 cps. In someembodiments the crosslinking molecule viscosity may be greater than1,000 cps if the reactive liquid diluent also includes a scaffoldmolecule or molecules that when combined with the crosslinking moleculewill provide a liquid mixture having a viscosity less than 1,000 cps.The crosslinking molecule number average molecular weight may forexample be at least about 200, at least about 500 or at least about 800,and may for example be less than about 3,000, less than about 2,000,less than about 1,500 or less than about 1,000. When added to a colorantor coating composition, the crosslinking molecule preferably providesless than 50 (viz., less than 500 ppm), less than 30, less than 10 orless than 5 grams per liter VOCs, as measured using the above-mentionedASTM D6886-14 procedure. The crosslinking molecule may, apart from anypolyoxyalkylene segment(s) that may be present, be a monomer and not anoligomer or polymer, or may be a monomer or oligomer and not a polymer.The crosslinking molecule may be linear or branched (e.g., having a starstructure), and may for example have 2, 3, 4, 5, 6 or more reactiveunsaturated sites, with 3 or more and more preferably 4 or more suchsites being preferred.

In one embodiment, the crosslinking molecule contains only carbon,hydrogen and oxygen atoms, or only carbon, hydrogen, nitrogen and oxygenatoms. In some embodiments, the crosslinking molecule does not containhydroxyl groups or carboxylic acid groups, and in other embodiments thecrosslinking molecule may contain hydroxyl groups or may containcarboxylic acid groups. In some embodiments, no other monomers oroligomers capable of crosslinking the binder are present other than thecrosslinking molecule, or other than the crosslinking molecule and acrosslinking scaffold molecule. In other embodiments, one or more othermonomers or oligomers capable of crosslinking the binder are present. Insome embodiments, the crosslinking molecule does not contain any or allof nitrogen atoms, phosphorus atoms or sulfur atoms. In someembodiments, the crosslinking molecule contains no reactive sites otherthan (meth)allyl ether groups, vinyl ether groups or (meth)acrylategroups. In some embodiments, the crosslinking molecule contains noreactive sites other than allyl ether groups. In some embodiments thecrosslinking molecule is not water-soluble, or is not a salt. In otherembodiments, the crosslinking molecule is water-miscible orwater-dispersible. If the crosslinking molecule is sufficientlywater-miscible or water-dispersible to reside in the aqueous phase of alatex coating composition tinted with the disclosed fluid colorant, thenthe crosslinking molecule desirably will leave the aqueous phase andcoalesce with the latex particles during film formation. In someembodiments the crosslinking molecule will assist in film coalescence bysuch latex coating compositions. Crosslinking molecules that assist incoalescence of a latex binder or other coating composition binder areespecially preferred, and preferably provide at least a 10° C., and morepreferably at least a 15° C., improvement in low temperaturecoalescence.

The crosslinking molecule preferably will solubilize or help solubilizethe disclosed optional pigment wetting agents or dispersing agents ifpresent. In some embodiments, the crosslinking molecule is useable inand compatible with universal colorants for tinting both waterborne andsolvent-borne coating compositions. Although minor amounts ofcrosslinking molecule coloration (e.g., yellow coloration) may bepermissible, especially for crosslinking molecules used to disperseyellow-hued or dark-hued colorants, the crosslinking molecule preferablyis colorless. Pigment dispersions containing the crosslinking moleculepreferably remain stable and non-settling when used as a colorantformulation or coating composition.

Representative crosslinking molecules include allyl ethers, methallylethers, vinyl ethers, acrylates, methacrylates, and mixtures thereof.Exemplary (meth)allyl ether crosslinking molecules include allylpentaerythritol (“APE”, or penta triallylether), di-(trimethylolpropanetetraallyl ether), di(trimethylolpropane tetramethallyl ether),di(pentaerythritol hexaallyl ether), di-(pentaerythritol hexamethallylether), pentaerythritol tetraallyl ether and pentaerythritoltetramethallyl ether. Exemplary vinyl ether crosslinking moleculesinclude di-trimethylolpropane tetravinyl ether), di-(pentaerythritolhexavinyl ether) and pentaerythritol tetravinyl ether. Exemplary(meth)acrylate-functional crosslinking molecules includedi-(trimethylolpropane tetraacrylate) and di-(trimethylolpropanetetramethacrylate). Exemplary materials that may be used as crosslinkingmolecules are also described in U.S. Pat. No. 7,728,068 B2 (Killilea etal. '068) and U.S. Pat. No. 7,923,513 B2 (Killilea et al. '513), wherevarious reactive diluents are employed as reaction media duringsynthesis of film-forming polymeric binders. Other exemplary materialsare described in British Patent No. 974,892 (Ilford), where variouspolyallyl ethers are combined with unsaturated polyesters to makeunpigmented compositions.

Crosslinking molecules with increased molecular weights may be preparedby combining lower molecular weight monomers in a variety of ways. Oneconvenient route involves an esterification reaction between ahydroxy-functional compound containing a suitable reactive unsaturatedsite or sites (e.g., a hydroxy-functional allyl ether) and an acid(preferably a di- or tri-acid) or an acid anhydride. Exemplaryhydroxy-functional allyl ethers include trimethylolethane mono- anddiallyl ether, trimethylolpropane mono- and diallyl ether, glycerolmono-, di- and triallyl ether, pentaerythritol mono-, di- and triallylether and sorbitol mono-, di-, tri-, tetra- and pentaallyl ether.Exemplary acids include maleic acid, fumaric acid, phthalic acid,5-nitroisophthalic acid, 5-sodiosulfoisophthalic acid, isophthalic acid,terephthalic acid, 2-nitroterephthalic acid, itaconic acid, oxalic acid,malonic acid, succinic acid, 2-methyl butanedioic acid, glutaric acid,adipic acid, citric acid, 2,4-dimethyl hexanedioic acid, pimelic acid,suberic acid, azelaic acid, sebacic acid, 5-norbornene-2,3-di-carboxylicacid, mesaconic acid, citraconic acid, chloromaleic acid, naphthalenedicarboxylic acid, 1,2,3-benzenetricarboxylic acid,1,2,4-benzenetricarboxylic acid, dimer fatty acid, trimer fatty acid,and other acids that will be familiar to persons having ordinary skillin the art. Exemplary acid anhydrides include maleic anhydride, phthalicanhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,methylhexahydrophthalic anhydride, trimellitic anhydride, pyromelliticanhydride, succinic anhydride, glutaric anhydride, β-methylglutaricanhydride, chlorendic anhydride, and other acid anhydrides that will befamiliar to persons having ordinary skill in the art. The ingredientsmay be combined using esterification procedures and equipment that willbe familiar to persons having ordinary skill in the art. When thereactants are liquids, they may simply be mixed in a suitably equippedreactor and heated for a sufficient time and temperature, under a streamof inert gas, until the desired degree of esterification has takenplace, as measured by the amount of water taken off from thecondensation reaction or by an acid value titration. If either reactantis a solid, it generally will also be desirable to first heat thereaction mixture to liquefy the solid reactants. At the conclusion ofthe reaction, it may be desirable to remove volatile unreacted startingmaterials or volatile nonfunctional side products using for examplevacuum stripping. Doing so may reduce the likelihood that such startingmaterials or side products will contribute to VOCs in the fluid colorantcomposition or finished coating composition.

Another route for making crosslinking molecules with increased molecularweights involves reacting an allyl chloride with a di- orhigher-hydroxyl-functional monomer, as described for example in theabove-mentioned British Patent No. 974,892 (Ilford).

In one embodiment, the resulting increased molecular weight crosslinkingmolecule has a central segment derived from an aromatic, aliphatic orcycloaliphatic polyacid (e.g. a diacid, triacid or tetraacid) or acidanhydride, with the central segment being linked to 2, 3, 4 or morependant reactive unsaturated sites. In a further embodiment, thecrosslinking molecule contains a segment derived from an aromatic,aliphatic or cycloaliphatic polyacid or acid anhydride, 2, 3, 4 or morependant reactive unsaturated sites, and substantially no other monomerresidues. In a particularly preferred embodiment, the crosslinkingmolecule is made by reacting a diallyl ether with succinic acid,succinic anhydride, isophthalic acid or isophthalic anhydride to providea tetrafunctional crosslinking molecule containing four allyl ethergroups.

The synthetic routes and reactants described above for making allylether-functional crosslinking molecules may readily be adapted usingtechniques that will be familiar to persons having ordinary skill in theart to make vinyl ether functional or (meth)acrylate functionalcrosslinking molecules having increased molecular weights.

The crosslinking molecule amounts in the disclosed fluid concentratesand colorants will to some extent depend upon the other ingredientspresent and may be empirically determined. Exemplary crosslinkingmolecule amounts are about 1 to about 60 wt. % crosslinking moleculebased on the total fluid concentrate or colorant weight.

A variety of scaffold molecules (including crosslinking scaffoldmolecules) may be used in the disclosed reactive liquid diluent.Preferably the scaffold molecule has a molecular weight sufficientlyhigh so that the scaffold molecule will be nonvolatilizing, and amolecular weight sufficiently low so that the scaffold molecule canserve (or participate in serving) as a dispersing medium for the pigmentparticles and without requiring an additional volatile carrier. Thescaffold molecule viscosity may for example be less than 1,000 cps, lessthan 500 cps, less than 300 cps, less than 200 cps or less than 100 cps.In some embodiments the scaffold molecule viscosity may be greater than1,000 cps if the reactive liquid diluent also includes a crosslinkingmolecule or molecules that when combined with the scaffold molecule willprovide a liquid mixture having a viscosity less than 1,000 cps. Thescaffold molecule number average molecular weight may for example be atleast about 200, at least about 500 or at least about 800, and may forexample be less than about 3,000, less than about 2,000, less than about1,500 or less than about 1,000. When added to a colorant or coatingcomposition, the scaffold molecule preferably provides less than 50,less than 30, less than 10 or less than 5 grams per liter VOCs, asmeasured using the above-mentioned ASTM D6886-14 procedure. The scaffoldmolecule may be linear or branched (e.g., having a star structure). Thescaffold molecule preferably has low or no crystallinity at the desiredfluid concentrate or colorant manufacturing or use temperatures (e.g.,room temperature), as crystallization may lead to increased viscosity orsolidification of the scaffold molecule. Scaffold molecules containingpolyoxyalkylene segments with molecular weights of 1,000 or more mayhave reduced tendency to solidify at room temperature if they have abranched rather than linear structure.

In one embodiment, the scaffold molecule contains only carbon, hydrogenand oxygen atoms, or only carbon, hydrogen, nitrogen and oxygen atoms.In some embodiments, the scaffold molecule does not contain hydroxylgroups or carboxylic acid groups, and in other embodiments the scaffoldmolecule may contain hydroxyl groups, carboxylic acid groups or bothhydroxyl groups and carboxylic acid groups. In some embodiments, thescaffold molecule does not contain any or all of nitrogen atoms,phosphorus atoms or sulfur atoms. The scaffold molecule may comprise,consist essentially of, or consist of one or more hydrophilic portions(e.g., polyoxyethylene segments) and one or more hydrophobic portions(e.g., saturated or polyunsaturated segments). The scaffold moleculemay, apart from any polyoxyalkylene segment(s), be a monomer and not anoligomer or polymer, or may be a monomer or oligomer and not a polymer.In one embodiment, the scaffold molecule contains 2, 3 or 4 sites ofethylenic unsaturation and 1 to 4 polyoxyalkylene segments. In anotherembodiment, the scaffold molecule contains no reactive sites aside fromthe sites of ethylenic unsaturation. In yet another embodiment, thescaffold molecule contains two or more conjugated carbon-carbon doublebonds.

In some embodiments, the scaffold molecule is water-miscible orwater-dispersible. In some embodiments, the scaffold molecule willsolubilize or help solubilize the optional pigment wetting agents ordispersing agents if present. In some embodiments, the scaffold moleculemay become anchored to pigment particles and thus may behave like aconventional pigment-affinic dispersing agent. In some embodiments, boththe scaffold molecule and an optional conventional pigment dispersingagent will become anchored to pigment particles. The scaffold moleculemay also serve as a humectant, especially when the scaffold moleculecontains sufficient polyoxyethylene content. In some embodiments, thescaffold molecule will be useable in and compatible with universalcolorants for tinting both waterborne and solvent-borne coatingcompositions. Although minor amounts of scaffold molecule coloration(e.g., yellow coloration) may be permissible, especially for scaffoldmolecules used in yellow-hued or dark-hued colorants, the scaffoldmolecule preferably is essentially colorless. Pigment dispersionscontaining the scaffold molecule preferably remain stable andnon-settling when used as a colorant formulation or coating composition.

The scaffold molecule may contain a variety of polyoxyalkylene segments,for example ethylene oxide, propylene oxide, ethylene oxide/propyleneoxide, polyoxyethylene or polyoxypropylene segments, withpolyoxyethylene segments being preferred. The polyoxyalkylene segmentsmay for example contain at least one, at least two, at least three, atleast four or at least five alkyleneoxy moieties, and may for examplecontain up to about 20, up to about 18 or up to about 15 alkyleneoxymoieties. The desired number of alkyleneoxy moieties may be determinedempirically. As a general guide, sufficient alkyleneoxy moieties shouldbe present so as to provide good pigment affinity. In addition, it isdesirable to avoid using so many alkyleneoxy moieties that the scaffoldmolecule forms a solid rather than a liquid at the desired fluidconcentrate or colorant manufacturing or use temperatures. In someembodiments, the polyoxyalkylene segments have a number averagemolecular weight of about 44 to about 2,000 or about 130 to about 1,200.

The scaffold molecule may contain a variety of hydrophobic segments. Inpreferred embodiments the hydrophobic segments also contain conjugatedcarbon-carbon double bonds. Such segments may for example be derivedfrom linear or branched polyunsaturated aliphatic compounds having atleast one conjugated carbon-carbon double bond. The conjugatedcarbon-carbon double bond may be but need not be pendant with respect tothe hydrophobic segment and may for example instead be located along abackbone chain.

In one exemplary embodiment, the scaffold molecule has a linearpolyoxyalkylene central segment (for example, a polyoxyethylene segment)joined by one or more ester linkages to one or more pendant unsaturatedfatty acid residues. Thus for example the scaffold molecule may be analkoxylated (e.g., ethoxylated) diester of a monounsaturated fatty acid,or may be an alkoxylated (e.g. ethoxylated) monoester of apolyunsaturated fatty acid. In another embodiment, the scaffold moleculehas a branched central segment (for example, a residue of a tri- orhigher-functional alcohol such as trimethylolpropane, pentaerythritol,dipentaerythritol, sorbitol or glycerol) joined by polyoxyalkylenesegments and ester linkages to three or more pendant unsaturated fattyacid residues.

Scaffold molecules that are also crosslinking scaffold molecules areespecially preferred. Exemplary such molecules may for example be madevia a straightforward and easily controllable esterification reactionbetween a variety of glycols, glycol ethers or alkoxylated alcohols anda variety of unsaturated acids having two or more conjugated backbonedouble bonds. In the resulting crosslinking scaffold molecules, ahydrophilic polyoxyalkylene segment will be joined to polyunsaturatedhydrophobic segments via one or more ester linkages. Exemplary glycolsand glycol ethers include ethylene glycol, diethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, tripropyleneglycol ethylene glycol methyl ether, diethylene glycol methyl ether,triethylene glycol methyl ether and higher alkyl ether analogs of thesealcohols such as their ethyl ether, propyl ether, butyl ether and2-ethyl hexyl ether analogs. Exemplary alkoxylated alcohols includepolyethylene glycols such as PEG 300, PEG 400, PEG 600, PEG 800 and PEG1000, methoxy polyethylene glycols such as MPEG 350, MPEG 500, MPEG550and MPEG 750 and propylene glycols such as PPG-9 and PPG-10, all ofwhich are available from Dow Chemical Company. A variety of tri- andhigher-functional alkoxylated alcohols may also be employed, such asalkoxylated alcohols derived from trimethylolpropane, pentaerythritol,dipentaerythritol, sorbitol or glycerol. Exemplary such tri- andhigher-functional alkoxylated alcohols include PLURIOL™ E 300, E 400, E600 and other PLURACOL E series alcohols (all available from BASF);Polyol 3165, Polyol 3940 and other 3000 series trifunctional alkoxylatedpolyols (all available from Perstorp), and Polyol 4360, Polyol 4640 andother 4000 series tetrafunctional alkoxylated polyols (also availablefrom Perstorp).

Polyunsaturated fatty acids are widely available at relatively low cost,and thus provide an especially convenient source for making crosslinkingscaffold molecules. The polyunsaturated acid may be aliphatic,cycloaliphatic, aromatic or combination thereof. Exemplarypolyunsaturated acids include omega-3 polyunsaturated fatty acids suchas hexadecatrienoic acid (all-cis 7,10,13-hexadecatrienoic acid),alpha-linolenic acid (all-cis-9,12,15-octadecatrienoic acid),stearidonic acid (all-cis-6,9,12,15,-octadecatetraenoic acid),eicosatrienoic acid (all-cis-11,14,17-eicosatrienoic acid),eicosatetraenoic acid (all-cis-8,11,14,17-eicosatetraenoic acid),eicosapentaenoic acid (all-cis-5,8,11,14,17-eicosapentaenoic acid),heneicosapentaenoic acid (all-cis-6,9,12,15,18-heneicosapentaenoicacid), docosapentaenoic acid (all-cis-7,10,13,16,19-docosapentaenoicacid), docosahexaenoic acid (all-cis-4,7,10,13,16,19-docosahexaenoicacid), tetracosapentaenoic acid(all-cis-9,12,15,18,21-tetracosapentaenoic acid) and tetracosahexaenoicacid (all-cis-6,9,12,15,18,21-tetracosahexaenoic acid); omega-6polyunsaturated fatty acids such as linoleic acid(all-cis-9,12-octadecadienoic acid), linoelaidic acid(CH₃(CH₂)₄CH═CHCH₂CH═CH(CH₂)₇COOH), gamma-linolenic acid(all-cis-6,9,12-octadecatrienoic acid), eicosadienoic acid(all-cis-11,14-eicosadienoic acid), dihomo-gamma-linolenic acid(all-cis-8,11,14-eicosatrienoic acid), arachidonic acid(all-cis-5,8,11,14-eicosatetraenoic acid), docosadienoic acid(all-cis-13,16-docosadienoic acid), adrenic acid(all-cis-7,10,13,16-docosatetraenoic acid), docosapentaenoic acid(all-cis-4,7,10,13,16-docosapentaenoic acid), tetracosatetraenoic acid(all-cis-9,12,15,18-tetracosatetraenoic acid) and tetracosapentaenoicacid (all-cis-6,9,12,15,18-tetracosapentaenoic acid); omega-9polyunsaturated fatty acids such as Mead acid(all-cis-5,8,11-eicosatrienoic acid); and other polyunsaturated fattyacids such as rumenic acid (9Z,11E-octadeca-9,11-dienoic acid),10E,12Z-octadeca-9,11-di enoic acid, α-calendic acid(8E,10E,12Z-octadecatrienoic acid), β-calendic acid(8E,10E,12E-octadecatrienoic acid), jacaric acid(8Z,10E,12Z-octadecatrienoic acid), α-eleostearic acid(9Z,11E,13E-octadeca-9,11,13-trienoic acid), β-eleostearic acid(9E,11E,13E-octadeca-9,11,13-trienoic acid), catalpic acid(9Z,11Z,13E-octadeca-9,11,13-trienoic acid), punicic acid(9Z,11E,13Z-octadeca-9,11,13-trienoic acid), rumelenic acid(9E,11Z,15E-octadeca-9,11,15-trienoic acid), α-parinaric acid(9E,11Z,13Z,15E-octadeca-9,11,13,15-tetraenoic acid), β-parinaric acid(all trans-octadeca-9,11,13,15-tretraenoic acid), bosseopentaenoic acid(5Z,8Z,10E,12E,14Z-eicosanoic acid), pinolenic acid((5Z,9Z,12Z)-octadeca-5,9,12-trienoic acid), podocarpic acid((5Z,11Z,14Z)-eicosa-5,11,14-trienoic acid), sorbic acid(2,4-hexadienoic acid), abietic acid((1R,4aR,4bR,10aR)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,4b,5,6,10,10a-decahydrophenanthrene-1-carboxylicacid) and mixtures thereof.

A variety of monounsaturated acids may also be used to prepare dimerizedor higher (e.g., branched) scaffold molecules, including diester ortriester scaffold molecules. Exemplary monounsaturated acids may bealiphatic, cycloaliphatic, aromatic or combination thereof, and includeelaidic acid (CH3(CH2)₇CH═CH(CH₂)₇COOH), erucic acid(CH₃(CH₂)₇CH═CH(CH₂)₁₁COOH), myristoleic acid(CH₃(CH₂)₃CH═CH(CH₂)₇COOH), oleic acid (CH₃(CH₂)₇CH═CH(CH₂)₇COOH),palmitoleic acid (CH₃(CH₂)₅CH═CH(CH₂)₇COOH), sapienic acid(CH₃(CH₂)₈CH═CH(CH₂)₄COOH), vaccenic acid (CH₃(CH₂)₅CH═CH(CH₂)₉COOH) andmixtures thereof.

A variety of natural products or derivatives thereof that are rich inpolyunsaturated or monounsaturated acids may also be employed to preparescaffold molecules. Exemplary such natural products or derivativesinclude canola oil, castor oil, corn oil, cottonseed oil, hemp oil, fishoil, gum rosin and maleinized gum rosin, linseed oil, oiticica oil,safflower oil, soybean oil, sunflower oil, tall oil fatty acid, tungoil, wheat germ oil and mixtures thereof.

Esterification procedures and equipment like those discussed above inconnection with the crosslinking molecule may be employed to makescaffold molecules and crosslinking scaffold molecules. Other syntheticroutes for making scaffold molecules, such as molecules with etherlinkages, amide linkages or other linkages between the hydrophilic andhydrophobic segments may also be employed, and will be familiar topersons having ordinary skill in the art. For example, polyunsaturatedfatty alcohols provide an alternative source for making scaffoldmolecules. Such alcohols can be alkoxylated (e.g., ethoxylated using forexample ethylene oxide) with appropriate reaction conditions andcatalysts to provide a polyunsaturated fatty alcohol alkoxylatecrosslinking scaffold molecule having a hydrophilic polyoxyalkylenesegment joined via an ether linkage to a polyunsaturated hydrophobicsegment.

Polyunsaturated fatty amines provide yet another source for makingscaffold molecules. Such amines can be alkoxylated (e.g., ethoxylatedusing for example ethylene oxide) with appropriate reaction conditionsand catalysts to provide polyunsaturated fatty amine alkoxylatecrosslinking scaffold molecules having a hydrophilic polyoxyalkylenesegment joined via a secondary amine linkage to a polyunsaturatedsegment derived from the fatty amine.

The scaffold molecule amounts in the disclosed fluid concentrates andcolorants will to some extent depend upon the other ingredients presentand may be empirically determined. Exemplary scaffold molecule amountsare about 1 to about 40 wt. % scaffold molecule based on the totalconcentrate or colorant weight.

Crosslinking scaffold molecules containing at least one hydrophilicpolyoxyalkylene segment, one or more hydrophobic segments (optionallyand preferably a polyunsaturated hydrophobic segment), and two or moreand preferably four or more (meth)allyl ether, vinyl ether or(meth)acrylate reactive sites, and having a viscosity less than 1,000cps, represent particularly preferred reactive liquid diluents. They maybe used by themselves to provide a reactive liquid diluent containing asingle molecular species, or may be used in combination with theabove-mentioned crosslinking molecules or the above-mentioned scaffoldmolecules to provide a reactive liquid diluent containing more than onemolecular species. For example, a crosslinking scaffold moleculereactive liquid diluent that contains polyoxyethylene segments topromote pigment dispersion and polyunsaturated segments and allyl ethergroups to enable IPN formation or crosslinking may be made via theesterification of two or more moles of a polycarboxylic acid oranhydride with one or more moles of a polyalkylene glycol (e.g.,polyethylene glycol) of suitable molecular weight, two or more moles ofa hydroxyl-functional mono- or preferably polyfunctional allyl ether,and one or more moles of a polyunsaturated fatty acid, to make areactive liquid diluent containing a hydrophilic polyoxyalkylene segmentjoined by ester linkages to two or more allyl ether groups and to one ormore hydrophobic segments containing a reactive unsaturated site in theform of a conjugated carbon-carbon double bond. The reaction conditionsfor this and other reactive liquid diluents desirably are controlled soas to provide products with low molecular weight, viscosity less than1,000 cps, and the capability to provide an IPN or crosslinking incoating compositions. Factors including the final viscosity, molecularweight, number of alkyleneoxy units, type and number of unsaturatedsites and the type and number of other reactive sites (e.g., allylether, vinyl ether or (meth)acrylate groups) may be varied to obtaingood pigment dispersing properties while maintaining low volatility andthe ability to form an IPN or crosslink with the binder, and whileavoiding plasticization of a coating film containing the reactive liquiddiluent.

Exemplary crosslinking scaffold molecules may also be prepared bymodifying the reactive surfactants shown in U.S. Pat. No. 9,051,341 B2(Palmer, Jr.) for use in emulsion polymerization. Preferred materialswill employ greater allyl group functionality and lower viscosity andequivalent weight per allyl group than the materials made in Palmer, Jr.

The reactive liquid diluent may for example represent at least about 10,at least about 20 or at least about 30 wt. % of a concentrate; at leastabout 1, at least about 5 or at least about 10 wt. % of a colorant; andat least about 1, at least about 5 or at least about 10 wt. % of acoating composition. The reactive liquid diluent may for example alsorepresent less than about 70, less than about 60 or less than about 50wt. % of a concentrate; less than about 60, less than about 50 or lessthan about 40 wt. % of a colorant; and less than about 60, less thanabout 50 or less than about 40 wt. % of a coating composition. As notedabove, the molecular specie(s) in the reactive liquid diluent having atleast three reactive unsaturated sites preferably represent the majorityby weight, and more preferably at least 60 wt. % or at least 70 wt. %,of the reactive liquid diluent.

A variety of conventional pigment wetting or dispersing agents mayoptionally be used in the disclosed fluid concentrates and colorants(viz., as the pigment wetting or dispersing agent if the reactive liquiddiluent does not stably disperse pigment, or as an added pigment wettingor dispersing agent if the reactive liquid diluent does dispersepigment). The disclosed fluid concentrates and colorants may containconventional pigment wetting agents but not conventional pigmentdispersing agents; conventional pigment dispersing agents but notconventional pigment wetting agents; or both conventional pigmentwetting agents and conventional pigment dispersing agents. Mixtures ofmore than one pigment wetting agent or more than one pigment dispersingagent may be employed. Exemplary conventional pigment wetting agentstypically are low molecular weight monomeric surfactants (for example,anionic, cationic or amphoteric surfactants), and exemplary conventionalpigment dispersing agents typically are higher molecular weightsurface-active or pigment particle affinic polymers (for example,polyelectrolyte dispersants such as maleic acid copolymers, andpolyurethanes or polyacrylates containing carboxylic acid, amine orisocyanate pigment affinic anchor groups). Preferably the pigmentwetting or dispersing agent is a so-called 100% solids material (viz.,it may be a liquid or a solid but is not supplied in a carrier and inparticular does not contain VOCs) and more preferably the pigmentwetting or dispersing agent is a liquid having a viscosity no greaterthan 4,000 cps, no greater than 2,000 cps, no greater than 1,000 cps, nogreater than 500 cps or no greater than 300 cps.

Representative pigment wetting agents are available from a variety ofsuppliers including Air Products and Chemicals (e.g., CARBOWET™ GA-210surfactant which has a viscosity of 80 cps, CARBOWET GA-221 surfactantwhich has a viscosity of 100 cps, DYNOL™ 607 superwetter which has aviscosity of 205 cps and DYNOL 800 superwetter which has a viscosity of230 cps); Dow Chemical Co. (e.g., CAPSTONE™ fluorosurfactants FS 31, FS34, FS 35, FS 61 and FS 64); and Stepan Company (e.g., STEPWET™ DOS-70surfactant which contains 70% active ingredients and has a viscosity of200 cps, and STEPWET DOS-70EA surfactant which contains 70% activeingredients and has a viscosity of 220 cps).

Representative pigment dispersing agents are also available from avariety of suppliers, and include various nonionic (e.g., ethoxylated)and anionic (e.g., non-ethoxylated salt) forms including agents from AirProducts and Chemicals, Inc. (e.g., SURFYNOL™ PSA336); Archer DanielsMidland Co. (e.g., ULTRALEC™ F deoiled lecithin); Ashland Inc. (e.g.,NEKAL™ WS-25-I, which is a sodium bis(2,6-dimethyl4heptyl)sulfosuccinate); BASF (e.g., DISPEX™ AA 4144, DISPEX ULTRA FA4425 which is a fatty acid-modified emulsifier having a viscosity of40,000 cps, DISPEX ULTRA FA 4420 which is a fatty acid-modifiedemulsifier and a dark brown liquid of unspecified viscosity, DISPEXULTRA FA 4431 which is an aliphatic polyether with acidic groups havinga viscosity of 350 cps, DISPEX ULTRA PA 4501 which is a fatty acidmodified polymer having a viscosity of 10,000 cps, DISPEX ULTRA PA 4510,EFKA™ PU 4010, EFKA PU 4047 which is a modified polyurethane, EFKA PX4300, EFKA ULTRA PA 4510 and EFKA ULTRA PA 4530 which are modifiedpolyacrylates, EFKA FA 4620 which is an acidic polyether having aviscosity of 1,400 cps, EFKA FA 4642 which is an unsaturated polyamideand acid ester salt having a viscosity of 2,000 cps, HYDROPALAT™ WE3135, HYDROPALAT WE 3136 and HYDROPALAT WE 3317 which are difunctionalblock copolymer surfactants terminating in primary hydroxyl groups andhaving respective viscosities of 375, 450 and 600 cps, and TETRONIC™ 901and TERTRONIC 904 which are tetrafunctional block copolymers terminatingin primary hydroxyl groups and having respective viscosities of 700 and320 cps); Borchers (e.g., BORCHI™ Gen 0451 which is a polyurethaneoligomer having a viscosity of about 30,000 cps, BORCHI Gen 0652 whichis an amine neutralized acrylic acid copolymer having a viscosity ofabout 75-300 cps, and BORCHI Gen 1252 and BORCHI Gen 1253 which areacrylic ester copolymers having respective viscosities of about1,500-3,500 and 50-300 cps); Byk-Chemie (e.g., BYK™ 156 which is asolution of an ammonium salt of an acrylate copolymer, DISPERBYK™ whichis a solution of an alkyl ammonium salt of a low-molecular-weightpolycarboxylic acid polymer, DISPERBYK-102 which is an acidic copolymer,DISPERBYK™-145 which is a phosphoric ester salt of a high molecularcopolymer with pigment affinic groups and a liquid of unspecifiedviscosity, DISPERBYK-190 which is a solution of a high molecular weightblock copolymer with pigment affinic groups, DISPERBYK-2013 which is astructured copolymer with pigment affinic groups having a viscosity of8,600 cps, DISPERBYK-2055 which is a copolymer with pigment affinicgroups and a liquid of unspecified viscosity, DISPERBYK-2060 which is asolution of a copolymer with pigment affinic groups having a viscosityof 3,600 cps, DISPERBYK-2061 which is a solution of a copolymer withpigment affinic groups having a viscosity of 491 cps, DISPERBYK-2091,DISPERBYK-2200 which is a high molecular weight copolymer with pigmentaffinic groups sold in solid form as pastilles and BYKJET™-9152 which isa copolymer with pigment affinic groups having a viscosity of 21,600cps); Clariant (e.g., DISPERSOGEN™ 1728 which is an aqueous solution ofa novolac derivative having a viscosity of 4,000 cps, DISPEROGEN 2774which is a novolac alkoxylate having a viscosity of 4,000 cps, GENAPOL™X 1003 and GENAPOL X 1005 which are fatty alcohol ethoxylates havingrespective viscosities of about 400 cps and 1,300 cps, HOSTAPAL BVconcentrate which is a sulfate ester having a viscosity of about 2,700cps); Cray Valley (e.g., SMA1440H which is an ammonia salt of a styrenemaleic anhydride copolymer solution); Dow Chemical Co. (e.g., the TAMOL™family of dispersants including TAMOL 165A and TAMOL 731A); Elementis(e.g., NUOSPERSE™ FA196 which has a viscosity of 1,200 cps); Lubrizol(e.g., SOLSPERSE™ 27000, SOLSPERSE 28000, SOLSPERSE 32000, SOLSPERSE39000, SOLSPERSE 64000, SOLSPERSE 65000, SOLSPERSE 66000, SOLSPERSE71000, SOLSPERSE M387, SOLPLUS™ R700 and SOLPLUS K500); Ethox Chemicals,LLC (e.g., the E-SPERSE™ family of dispersants and ETHOX™ 4658); Evonik(e.g., TEGO™ DISPERS 656, TEGO DISPERS 685, TEGO DISPERS 750W and TEGODISPERS 757W); Rhodia Solvay Group (e.g., ABEX 2514 and ABEX 2525 whichare nonionic surfactants, RHODACAL™ IPAM which is isopropyl aminedodecylbenzene sulfonate having a viscosity of 10,000 cps, RHODAFAC™RS-710 which is a polyoxyethylene tridecyl phosphate ester, and theRHODOLINE™ family of dispersants including RHODOLINE 4170 and RHODOLINE4188); Sasol Wax GmbH (e.g., ADSPERSE™ 100, ADSPERSE 500 and ADSPERSE868) and Stepan Company (e.g., G-3300 which is an isopropyl amine saltof an alkyl aryl sulfonate having a viscosity of about 6000 cps,POLYSTEP™ A-15 which is a sodium dodecylbenzene sulfonate having aviscosity of about 85 cps, POLYSTEP B-11 and POLYSTEP B-23 which areethoxylated ammonium lauryl ether sulfates respectively containing 4 or12 moles of ethylene oxide and having respective viscosities of 66 and42 cps, and POLYSTEP B-24 which is sodium lauryl sulfate having aviscosity of 100 cps).

The optional conventional wetting agent or dispersing agent amounts inthe disclosed fluid concentrates and colorants may as noted above dependon whether the disclosed reactive liquid diluent will by itself alsostably disperse the pigment particles, may also depend upon the otheringredients present, and may be empirically determined. The chosenamounts typically will vary depending upon on the actual surface area ofthe pigment particles or combination of pigment particles to be wettedor dispersed. As a general rule, the smaller the pigment particle size,the higher the actual surface area, hence the larger the total pigmentsurface area over which the wetting or dispersing agent may need to bedistributed. A curve may be plotted to measure the reduction inviscosity as a wetting agent or dispersing agent is added incrementallyto a pigment slurry, with the minimum viscosity indicating a recommendeddosage level. Alternatively, or as a starting guide, exemplary pigmentwetting agent or dispersing agent amounts are about 5 to about 115 wt. %wetting agent or dispersing agent based on pigment weight.

The disclosed fluid concentrates and colorants and their associatedmethods may contain or employ (but need not contain or employ) otheringredients, and may instead consist of or consist essentially ofpigment particles, the reactive liquid diluent and optional additionalpigment wetting or dispersing agents. The concentrates and someembodiments of the colorants may preferably contain less than about 2wt. %, less than about 1 wt. %, less than about 500 ppm, less than about100 ppm, or less than about 10 ppm of other ingredients based on theconcentrate or colorant composition weight.

The disclosed concentrates and colorants may optionally contain (andtheir associated methods may optionally employ) water or other carriers.Preferably water and other carriers are not present in the concentratesso as to provide a high pigment content and to afford greaterflexibility when making downstream products. Water, if used, may be tap,deionized, distilled, reverse osmosis or recycled water. Exemplary wateramounts are for example about 1 to less than 5 wt. % of a concentrateand about 1 to about 50 wt. % of a colorant, and with amounts incolorants preferably being less than 15 wt. %, less than 10 wt. % orless than 5 wt. %. Exemplary other carriers include alcohols (e.g.,ethanol); esters (e.g., butyl acetate, methoxypropyl acetate andpropylene glycol monomethyl ether acetate); ketones (e.g., acetone,methyl ethyl ketone, methyl isoamyl ketone and methyl isobutyl ketone;ester/ketone mixtures (e.g., ethyl 3-ethoxypropionate/methyl ethylketone mixtures); UV curable monomers (e.g., acrylate or vinyl ethermonomers); aliphatic solvents (e.g., white spirit, mineral spirit,petroleum distillates, paraffin solvent or vegetable oils); aromaticsolvents (e.g., toluene, xylene, Aromatic 100 and other naphthasolvents); mixtures of aromatic solvents and ethers; and universalsolvents that will work with both latex and oil-based paints (e.g.,ethylene glycol, propylene glycol, hexylene glycol and glycol/watermixtures). Such other carriers, if used, preferably are used in very lowamounts (e.g. less than 5 wt. %, no more than 2 wt. % or no more than 1wt. % of the fluid concentrate or colorant) so as to minimize VOCemissions and avoid plasticization of coating composition films.

When molecular species in the disclosed reactive liquid diluent system(e.g., when a crosslinking molecule and scaffold molecule are mixed withone another), the molecular species preferably form a uniform mixturethat is a Newtonian liquid at room temperature. When reactive liquiddiluent containing a single molecular species is employed, it likewisepreferably is a Newtonian liquid at room temperature. A mixture ofreactive liquid diluent molecular species, or a reactive liquid diluentcontaining only a single molecular species, preferably has a viscosityless than 500 cps, and more preferably less than 300 cps, less than 200cps or less than 100 cps.

When compared to traditional colorant dispersant blends containing amixture of a polyethylene glycol and an alcohol ethoxylate surfactant,the reactive liquid diluent preferably provides an improvement in one ormore of VOC reduction, pigment fineness of grind, colorant dispenser tipdrying resistance, freeze-thaw resistance, tinted paint viscosity drop,tinted paint rub-up resistance, low temperature coalescence, open timeor wet edge maintenance during application, drying time afterapplication, tack resistance during cure or block resistance after cure.In preferred embodiments the disclosed reactive liquid diluent enables apaint or colorant manufacturer to reduce the amounts of other requiredraw materials (e.g., conventional carriers, dispersing agents,coalescents or humectants) and the number of in-process intermediates,that may otherwise need to be employed in a paint, stain or colorantmanufacturing facility.

The disclosed fluid concentrates, colorants and coating compositions maycontain a metal drier or other catalyst to catalyze reaction (e.g.,chain extension or crosslinking) of reactive unsaturated sites (e.g.,(meth)allyl ether groups, vinyl ether groups, (meth)acrylate groups, orconjugated carbon-carbon double bonds) that may be present in thereactive liquid diluent. The disclosed reaction may be accelerated bythe presence of oxygen, such as may be available when a coatingcomposition film coalesces, and in such instances could be said toprovide oxidative curing of the disclosed reactive liquid diluent. Thecatalyst may be included in a colorant (if care is taken to control thecatalyst amount and if need be meanwhile to exclude air or othersubstances that might promote premature gelation), may be added to oradded along with the colorant as a separate component at the time ofpoint-of-sale tinting, or may be incorporated in a base coatingcomposition. When the base coating composition is an alkyd paint, thenthe metal driers normally included in such paints can be used, withappropriate adjustment of the metal drier amount if need be, to catalyzeIPN formation or crosslinking by the disclosed reactive liquid diluent.Typically, a combination of metal driers will be employed in order toprovide desirable surface and subsurface cure characteristics. Exemplarymetal driers include metal soaps or coordination compounds made byreacting a metal such as cobalt, calcium, zirconium, manganese, iron orcerium with an appropriate acid. Representative metal driers will befamiliar to persons having ordinary skill in the art, and are availablefrom suppliers including Allnex (e.g., ADDITOL™ VXW 4940 which containscobalt, barium and zirconium, ADDITOL VXW 6206 and ADDITOL VXW 6560which each contain cobalt, lithium and zirconium, and CYCAT™ VXK 6395which is a para-toluene sulfonic acid amino blocked acidic catalyst),Dura Chemicals, Inc. (e.g., DRICAT™ 408 which is a cobalt-free drier,DUROCT™ 5% WDX and DUROCT COBALT 12% NX which each contain cobalt,ZIRCONIUM 24% SYN NUXTRA™ which contains zirconium, and XL-DRI™ 69600which contains cobalt, manganese and vanadium), Huls America, Inc.,(e.g., NUXTRA™ Zirconium 24% which contains zirconium), King Industries(e.g., NACURE™ 155 which is a dinonylnaphthalene disulfonic blocked acidcatalyst, NACURE 2500 which is a para-toluene sulfonic acid blocked acidcatalyst, NACURE 4000 which is a phosphate acid catalyst and NACUREXC-305 which is an acid catalyst), OMG Borchers GmbH (e.g., OMG™ 12%Manganese which contains manganese, and OXY-COAT™ which is an irondrier) and Troy Corporation (e.g., TROYMAX™ Zinc 16 which is a zinc saltmetal carboxylate solution). As an alternative or supplement to use ofthe disclosed metal drier, formation of the disclosed IPN orcrosslinking may be initiated or catalyzed using a variety of other freeradical cure promoters. Exemplary such promoters include free radicalgenerating catalysts, photoinitiators (e.g., UV or visible lightphotoinitiators), thermal initiators and other catalysts that will befamiliar to persons having ordinary skill in the art. Approaches that donot require the use of a catalyst, such as electron beam cure, mayinstead or also be employed if desired. When a catalyst is used, thecatalyst amount typically will depend upon the chosen catalyst and theamount(s) of reactive liquid diluent components in the disclosed fluidconcentrates and colorants, and may be empirically determined. Apreferred catalyst amount will provide a hard, clear, tack-free filmwhen the reactive liquid diluent and catalyst are mixed together anddrawn down into a thin film using a wire-wound rod or other suitableapplicator such as the above-mentioned BIRD bar applicator. Exemplarycatalyst amounts, based on a comparison of the total crosslinkingmolecule and scaffold molecule weight in a fluid colorant or aconcentrate to the actual or expected resin solids weight in a coatingcomposition, are about 0.05 to about 0.25 wt. % catalyst, about 0.025 toabout 0.125 wt. % catalyst, and about 0.025 to about 0.25 wt. %catalyst.

The disclosed fluid concentrates and colorants may optionally include afurther crosslinking agent to assist in IPN formation or crosslinking.For example, if available secondary amine groups are present in acrosslinking molecule or scaffold molecule, then a polyisocyanate (e.g.,a diisocyanate) may be added as a separate tinting ingredient or as acomponent of a base coating composition so as to promote additionalcrosslinking. Other further crosslinking agents that will be familiar topersons having ordinary skill in the art may be employed for reactionwith epoxy groups, acetoacetyl groups, aldehyde groups and otherfunctional groups that may be included in the crosslinking molecule,scaffold molecule or binder. It may however be desirable to avoid theuse of functional groups that might compromise the performance ofcommonly-employed coating compositions or commonly-employed coatingcomposition ingredients, such as phosphate groups, primary amine groupsor thiol groups.

The disclosed fluid concentrates and colorants may optionally includeadditional low viscosity components to modulate (e.g. reduce) viscosity.Exemplary such viscosity modulators include non-reactive or reactivematerials of less than 20 cps viscosity. Desirably, such viscositymodulators, if used, are employed in very low amounts, e.g. less than 5wt. %, less than 3 wt. % or less than 1 wt. % of a colorant or less than20 wt. % or less than 10 wt. % of a concentrate.

The disclosed fluid concentrates and colorants may optionally include avariety of other adjuvants including extender particles, thickeners andother rheology modifiers to increase viscosity, humectants to discouragedispenser tip drying, defoamers, mildewcides or biocides to discouragemicrobial growth, and other adjuvants or mixtures thereof that will befamiliar to persons having ordinary skill in the art. These otheradjuvants may be added along with the pigment, or may be added after thepigment particles have been dispersed. As discussed above, the disclosedreactive liquid diluent may serve as a humectant, and accordingly mayenable reduction in or even complete replacement of conventionalhumectants. For example, reactive liquid diluents containing a scaffoldmolecule can improve dispenser tip dry resistance in automated or manualcolorant dispensing equipment, and thereby enable a reduction in the useof conventional humectants in the colorant or base paint. The resultingtinted paints may also exhibit reduced tinted paint viscosity drop andone or both of reduced tack or improved block resistance.

Extender particles typically will be used in most or all of thedisclosed fluid colorants. In some embodiments, they will be used in thedisclosed concentrates, and in other embodiments will not be present insuch concentrates and instead will be added later when manufacturingfluid colorants or finished coating compositions from such concentrates.Exemplary extender particles include calcium carbonate, calcium sulfate,barium sulfate, mica, clay, calcined clay, feldspar, nepheline, syenite,wollastonite, diatomaceous earth, alumina silicates, non-film formingpolymer particles, aluminum oxide, silica, talc, mixtures thereof andother materials that will be familiar to persons having ordinary skillin the art. The chosen extender pigment types and amounts may varywidely and normally will be empirically determined using techniques thatwill be familiar to persons having ordinary skill in the art.

Exemplary thickeners and other rheology modifiers include sedimentationinhibitors, hydrophobic ethoxylated urethane resin (HEUR) thickeners,hydrophobically-modified, alkali-soluble or alkali-swellable emulsion(HASE) thickeners), cellulosic thickeners, polysaccharide thickeners andmixtures thereof. Exemplary commercially-available rheology modifiersinclude NATROSOL™ 250 and the AQUAFLOW™ series from Ashland, ATTAGEL™ 50from BASF Corp., the CELLOSIZE™ series and UCAR POLYPHOBE™ T-900 andT-901 from Dow Chemical Co., BENTONE™ AD and BENTONE EW from ElementisSpecialties, LATTICE™ NTC-61 from FMC Biopolymer and ACRYSOL™ RM-6,ACRYSOL RM-8, ACRYSOL RM-12W and ACRYSOL RM-2020NPR all from Rohm &Haas. The chosen rheology modifier types and amounts may vary widely andnormally will be empirically determined using techniques that will befamiliar to persons having ordinary skill in the art

In some embodiments, adjuvants such as defoamers, fungicides,mildewcides or biocides may optionally be included in the disclosedfluid concentrates or colorants, and may instead or in addition beincluded in a coating composition mixed with or made from suchconcentrates or colorants. Exemplary defoamers, fungicides, mildewcidesand biocides are discussed below in connection with the disclosedcoating compositions. In any event, the chosen amounts for theseadjuvants may vary widely and normally will be empirically determinedusing techniques that will be familiar to persons having ordinary skillin the art.

The disclosed concentrates may be mixed (e.g., milled) using a varietyof devices that will be familiar to persons having ordinary skill in theart. Exemplary such devices include horizontal bead mills, vertical beadmills, basket mills, roller mills, stator mixers and high speeddispersers.

The disclosed concentrates and colorants preferably are substantiallyfree of, and more preferably do not contain, film-forming polymericbinders. As noted above, the disclosed colorant contains less than acontinuous film-forming amount of the film-forming polymeric binder.This amount may be evaluated using a comparison composition made bymixing the binder with the pigment particles, extender particles andother coating composition adjuvants present in the colorant, using theamounts employed in such colorant, but excluding the disclosed reactiveliquid diluent from such mixture, and determining whether the pigmentlevel in the mixture is above or below the critical pigment volumeconcentration (CPVC). For a colorant containing less than a continuousfilm-forming amount of the film-forming polymeric binder, the pigmentamount in the comparison composition will be above CPVC and a drawdownof the comparison composition will form a discontinuous rather than acontinuous film.

A variety of materials that will be familiar to persons having ordinaryskill in the art may be combined with the above-described fluidconcentrates or colorants to make the disclosed coating compositions.The resulting coating compositions may have a variety of surfacecharacteristics (e.g., a flat, satin, semigloss or gloss finish) and maybe transparent (viz., containing only a relatively small amount ofpigment and having low hiding power), semitransparent or opaque. Opaquecompositions may for example have a contrast ratio greater than 96%,greater than 98%, greater than 99% or greater than 99.5%. Properties ofthe final coating composition may also be adjusted by adding additionalquantities of the disclosed reactive liquid diluent to a paint duringpaint manufacturing, or by using a point-of-sale colorant array in whichtwo or more colorants in the array (e.g., two white colorants) containsimilar pigments but different relative amounts of the reactive diluentliquid and pigment.

A variety of film-forming polymeric binders may be used in the disclosedcoating compositions. Exemplary binders include latex polymers andsolution polymers, e.g., acrylic copolymers, styrene/acrylic copolymers,vinyl acetate copolymers, vinyl acetate/acrylic copolymers, vinylversatic acid ester/acrylic copolymers, ethylene/vinyl acetatecopolymers, styrene/butadiene copolymers, polyesters, alkyd paints,drying oil modified polymers such as polyesters and polyurethanes,polyamides, epoxy esters, polyureas, polyurethane dispersions,polysiloxanes, silicones, fluorinated copolymers such as vinylidenefluoride, binders used in 100% solids UV or visible light curablesystems, and blends of any of the above polymeric binders. The bindermay include a component or components of a multicomponent (e.g., twocomponent) reactive system such as a component of anisocyanate-polyamine, isocyanate-polyol, isocyanate-amine,epoxy-polyamine, carbodiimide-polyacid, aziridine-polyacid,melamine-polyol, or urea formaldehyde-polyol coating system. The glasstransition temperature for the polymeric binder may for example be about−130 to about 350° C., preferably about −20 to about 150° C., and morepreferably about 0 to about 100° C. The binder may for example representabout 5 to about 90 volume percent of the dried coating volume. Thevolume solids, as defined by the fractional volume of dry ingredients inan as-supplied coating composition, may for example represent about 5 toabout 80 volume percent of the coating composition. The pigment volumeconcentration (PVC) may for example represent about 0.1 to about 95volume percent of the coating. In some embodiments, the PVC desirably isabout 0.1 to about 30 volume percent, about 0.5 to about 25 volumepercent, or about 1 to about 25 volume percent of the coating. Thecoating composition viscosity may for example be about 10 to 100,000cps.

In addition to the polymeric film forming binder and the colorantadjuvants already discussed above, the disclosed finished coatingcompositions may contain a variety of other adjuvants commonly used incoating compositions. These ingredients preferably are selected so thatthe coating composition will be a low VOC composition. Preferably thecoating composition will contain less than about 10 g/L, more preferablyless than about 5 g/L and most preferably less than about 500 ppm, lessthan about 50 ppm or less than about 10 ppm volatile organic compounds.Representative coating composition adjuvants are described in Koleske etal., Paint and Coatings Industry, April, 2003, pages 12-86, and areavailable from a wide variety of suppliers including Air Products andChemicals, Ashland, BASF, Buckman Laboratories, Inc., BYK-Gardner USA,Cognis, Cytec, Dow Chemical Co., Evonik, Rohm and Haas, Rhone Poulencand Troy Corporation. Exemplary coating composition adjuvants includeanti-cratering agents, biocides, coalescents, cosolvents, curingindicators, defoamers, fungicides, heat stabilizers, leveling agents,light stabilizers, mildewcides, optical brighteners, preservatives,surfactants, ultraviolet light absorbers, waxes and the like. The typesand amounts of these and other coating composition adjuvants typicallywill be empirically selected. Representative choices for several suchcoating composition adjuvants are set out below.

Exemplary biocides or mildewcides include BUSAN™ 1292 from BuckmanLaboratories, Inc., NOPCOCIDE™ N-40D from Cognis, KATHON™ LX from Rohm &Haas, and POLYPHASE™ 663, POLYPHASE 678 and POLYPHASE PW-40 from TroyCorporation.

Coalescents may assist in coalescing a film-forming polymer (for examplean emulsion polymer) into a continuous film. As discussed above, thedisclosed reactive liquid diluent may serve as a coalescent, andaccordingly may enable reduction in, or even complete replacement of,conventional coalescents. After coating cure, formation by the reactiveliquid diluent of the disclosed IPN within, or crosslinks with, thecured binder film may provide reduced post-cure VOC levels compared tothe use of conventional coalescents. Exemplary conventional coalescentsinclude benzoates such as alkyl benzoates, monobenzoates anddibenzoates; hexanoates such as OPTIFILM™ 400 tri(ethylene glycol)bis(2-ethylhexanoate) from Eastman Chemical Co.; dioctyl maleate; oleicacid propylene glycol esters such as EDENOL™ EFC-100 from Cognis havingthe formula HOCH(CH₃)CH₂OC(O)(CH₂)₇CH═CH(CH₂)₇CH₃); UCAR Filmer IBT,UCAR n-propyl propionate, UCAR n-butyl propionate and UCAR n-pentylpropionate from DOW Chemical Co.; ester alcohols such as TEXANOL™ esteralcohol from Eastman Chemical Co. (viz., 2,2,4-trimethyl-1,3-pentanediolmonoisobutyrate, CAS NO. 24265-77-4); materials discussed in U.S. Pat.Nos. 6,762,230 B2, 7,812,079 B2 and 8,110,624 B2 (collectively,Brandenburger et al.) and in U.S. Pat. No. 8,106,239 B2 (Zhou et al.)and U.S. Pat. No. 8,394,496 B2 (Foster et al.), in U.S. Published PatentApplication No. US 2009/0149591 A1 (Yang et al.); mixtures thereof andthe like. Low VOC or no-VOC coalescents are preferred, and dioctylmaleate is especially preferred. When a conventional coalescent isemployed, the coating compositions preferably contain about 0.05 toabout 10 or about 0.05 to about 5 wt. % conventional coalescent based onthe final coating composition weight. If desired, the reactive liquiddiluent or conventional coalescent(s) may be included in the colorantbut not in the base coating composition of a point-of-sale tintingsystem. In an additional embodiment, a separate dispensing canister in amulti-canister point-of-sale colorant dispenser could be dedicated to anuntinted composition containing the reactive liquid diluent by itself orwith a conventional coalescent. Additions from this dedicated canistercould be used to adjust the amount of coalescent in the final tintedcoating composition, thus permitting adjustment of coalescent contentacross a range of base coating composition formulations.

Cosolvents may assist in mixing or coating a composition; may speed up,retard or otherwise change the time or emissions associated with drying;may improve wet edge properties or overlap characteristics; may improvefreeze-thaw protection, or may provide or improve other features, andgenerally will not be retained in a film of the dried, cured orotherwise hardened coating composition. A chosen cosolvent preferably isa non-HAPS, low VOC material and not an ozone depleter. Cosolvents thatare exempted from categorization as VOCs by the EPA (viz., so-called“exempt solvents” such as parachlorobenzotrifluoride, acetone, methylacetate, tertiary butyl acetate and volatile methyl siloxanes) are alsopreferred. Other exemplary cosolvents include glycols (e.g., ethyleneglycol and diethylene glycol), glycol ethers (e.g., DOWANOL™ DPM andButyl CELLOSOLVE™ from Dow Chemical Co.), alcohols (e.g., n-propanol,isopropanol, n-butanol, isobutanol, 2-methyl butanol, isoamyl alcoholand other primary amyl alcohol isomers, n-pentanol, 2-ethylhexanol,4-hydroxy-2,6,8-trimethylnonane and diisobutyl carbinol), esters andester alcohols (e.g., isopropyl acetate; n-butyl acetate; isobutylacetate; n-propyl acetate; primary amyl acetate mixed isomers, and UCAR™Ester EEP from Dow Chemical Co.), ketones (e.g., diisobutyl ketone andECOSOFT™ Solvent IK from Dow Chemical Co.), CARBOWAX™ 300 and CARBOWAX600 polyethylene from Dow Chemical Co., mixtures thereof and the like.When a cosolvent is present, the coating compositions preferably containabout 0.1 to about 10 or about 2 to about 5 wt. % cosolvent based on thefinal coating composition weight.

Exemplary light stabilizers include hindered amines such as TINUVIN™123-DW and TINUVIN 292 HP from Ciba Specialty Chemicals. Exemplaryultraviolet light absorbers include TINUVIN 234 and TINUVIN 1130 fromCiba Specialty Chemicals. Exemplary waxes include AQUACER™ 593 fromAltana, HYDROCER™ 303 from Shamrock Technologies, Inc. and MICHEM™Emulsion 32535 from Michelman, Inc.

Exemplary surfactants include anionic, amphoteric and nonionicmaterials. Commercially-available surfactants include the TAMOL™ seriesfrom Dow Chemical Co., nonyl and octyl phenol ethoxylates from DowChemical Co. (e.g., TRITON™ X-45, TRITON X-100, TRITON X-114, TRITONX-165, TRITON X-305 and TRITON X-405) and other suppliers (e.g., theT-DET N series from Harcros Chemicals), alkyl phenol ethoxylate (APE)replacements from Dow Chemical Co., Elementis Specialties, Inc. andothers, various members of the SURFYNOL™ series from Air Products andChemicals, Inc. (e.g., SURFYNOL 104, SURFYNOL 104A, SURFYNOL 104BC,SURFYNOL 104DPM, SURFYNOL 104E, SURFYNOL 104H, SURFYNOL 104PA, SURFYNOL104PG50, SURFYNOL 104S, SURFYNOL 2502, SURFYNOL 420, SURFYNOL 440,SURFYNOL 465, SURFYNOL 485. SURFYNOL 485W, SURFYNOL 82, SURFYNOL CT-211,SURFYNOL CT-221, SURFYNOL OP-340, SURFYNOL PSA204, SURFYNOL PSA216,SURFYNOL PSA336, SURFYNOL SE and SURFYNOL SE-F), various fluorocarbonsurfactants from 3M, E. I. DuPont de Nemours and Co. and othersuppliers, and phosphate esters from Ashland, Rhodia and othersuppliers. When a surfactant is present, the coating compositionspreferably contain about 0.1 to about 10 wt. % and more preferably about1 to about 3 wt. % surfactant based on the total composition weight.

The disclosed fluid colorants and coating compositions may be packagedin any convenient packaging suitable for storing a desired quantity ofthe colorant or coating composition without premature gelation, undueseparation or other undesirable degradation during storage. Exemplarypackaging containers for colorants include bottles, cans, cartridges,jars and pouches sized to fit available manual or automated colorantdispensers. Exemplary packaging containers for coating compositionsinclude cans, pails, bottles, drums, totes and tanks. The disclosedcoating compositions may be factory-applied to substrates such asbuilding components at a manufacturing site; may be supplied toprofessional or consumer point-of-sale outlets and used as is orcustom-tinted with the disclosed fluid colorants; or may be supplied toend users and applied onsite to finished articles, e.g., as paints orpigmented stains for use on interior or exterior building components(for example, interior or exterior walls, trim, siding, floors,ceilings, roofing and cabinetry), furniture and other paintable orstainable objects and surfaces.

The disclosed coating compositions may be applied to a variety ofsubstrates including metals (including aluminum, brass, copper, iron,pot metal, steel, tin and zinc), woods (including engineered woods,impregnated woods and wood-derived materials), plastics (includingthermoplastics and thermosets), composites, cements, cement fiberboard,stone, glass, and other materials that will be familiar to personshaving ordinary skill in the art. The disclosed coating compositionshave particular value as highly-pigmented topcoats. They may also beused as pigmented or unpigmented primers. In preferred embodiments, theproperties (for example, storage stability including stable viscosity,freedom from settling or separation, wet edge maintenance, drying time,blocking resistance, water sensitivity, opacity, contrast ratio, hidingpower, color stability or minimal color change) of tinted coatingcompositions containing the disclosed reactive liquid diluent will be asgood as or better than the properties of corresponding untinted ortinted coating compositions that do not contain the reactive liquiddiluent.

The disclosed coating compositions may be applied using a variety ofmethods that will be familiar to persons having ordinary skill in theart, including spraying (e.g., air-assisted, airless or electrostaticspraying), brushing, roller coating, flood coating, curtain coating,coil coating, dipping and electrostatic coating. The compositions may beapplied at a variety of wet film thicknesses. Preferably the wet filmthickness is such as to provide a dry film thickness of about 13 toabout 260 μm (about 0.5 to about 10 mil) and more preferably about 25 toabout 75 μm (about 1 to about 3 mil) for the dried coating. The appliedcoating may be cured by allowing it to air dry or by accelerating curingusing a variety of drying devices (e.g., ovens) that will be familiar topersons having ordinary skill in the art. Exemplary interiortemperatures for such drying devices are about 30° to about 65° C., andexemplary heating times are less than 60 minutes, less than 45 minutes,less than 30 minutes, less than 15 minutes, less than 10 minutes, lessthan 6 minutes or less than 5 minutes. Heating times will tend todecrease with increased temperature, increased airflow, decreasedhumidity or decreased coating thickness.

The invention is further illustrated in the following non-limitingexamples, in which all parts and percentages are by weight unlessotherwise indicated.

Example 1

Crosslinking Molecule A

Into a 4 necked, 3 liter round bottom flask was charged 449.4 grams (2.1moles) of trimethylolpropane diallyl ether 90 from Perstorp, 100 grams(1 mole) of succinic anhydride and 0.5 grams of butyl stannoic acid. Thecontents were heated up to 190° C. under a nitrogen sparge andesterified to an acid value less than 5 to form a tetraallylether-functional crosslinking molecule. The reactor contents were thenvacuum stripped to remove volatile components. The crosslinking moleculehad the following characteristics: % Non volatiles=95.4; Viscosity=60cps; Color=2 Gardner. The crosslinking molecule was designated asCrosslinking Molecule A.

Crosslinking Molecule B

Using the method employed for Crosslinking Molecule A, the flask wascharged with 449.4 grams (2.1 moles) of trimethylolpropane diallylether, 166 grams (1 mole) of isophthalic acid and 0.6 grams of butylstannoic acid. The contents were heated up to 210° C. under a nitrogensparge and esterified to an acid value less than 5 to form a tetraallylether-functional crosslinking molecule. The reactor contents were thenvacuum stripped to remove volatile components. The crosslinking moleculehad the following characteristics: % Non volatiles=96.6; Viscosity=400cps; Color=2 Gardner. The crosslinking molecule was designated asCrosslinking Molecule B.

Example 2

Scaffold Molecule A

Into a 4 necked, 3 liter round bottom flask was charged 600 grams (1mole) of CARBOWAX polyethylene glycol PEG600 (Dow Chemical Co.), 560grams (2 moles) of PAMOLYN™ 200 linoleic acid (Eastman Chemical Co.) and1.1 grams of butyl stannoic acid. The contents were heated up to 220° C.under a nitrogen sparge and esterified to an acid value less than 5 toform a linear scaffold molecule with the following characteristics: %Non volatiles=99.3; Viscosity=110 cps; Color=8 Gardner. The scaffoldmolecule was designated as Scaffold Molecule A.

Scaffold Molecule B

Using the method employed for Scaffold Molecule A, the flask was chargedwith 990 grams (about 1 mole) of Polyol 3165 (a 1,014 molecular weightethoxylated trimethylolpropane triol available from Perstorp), 560 grams(2 moles) of PAMOLYN 200 linoleic acid and 1.5 grams of butyl stannoicacid. The contents were heated up to 220° C. under a nitrogen sparge andesterified to an acid value less than 5 to form a linear scaffoldmolecule with the following characteristics: % Non volatiles=99.6;Viscosity=150 cps; Color=10 Gardner. The scaffold molecule wasdesignated as Scaffold Molecule B.

Scaffold Molecule C

Into a 4 necked, 3 liter round bottom flask was charged 220.2 grams (2.2moles) succinic anhydride and 700 grams (2 moles) CARBOWAX MPEG 350 (DowChemical Company). The contents were heated to 150° C. under a nitrogensparge and esterified to a target acid value of 146, giving a monoesterintermediate with the following characteristics: Acid value=145, % Nonvolatiles=98.7; Viscosity=182 cps; Color=1 Gardner.

The flask may be cooled to room temperature and 622.05 gramstrimethylolpropane diallyl ether 90 (Perstorp), 1.5 grams butyl stannoicacid and methyl isobutyl ketone (MIBK) added to the flask. The contentsmay be heated to 190° C. under a nitrogen sparge and esterified to anacid value less than 5 at which point MIBK and excess trimethylolpropanediallyl ether 90 may be removed via nitrogen followed by vacuumstripping. The resulting scaffold molecule would be designated asScaffold Molecule C.

Scaffold Molecule D

Using the method employed for Scaffold Molecule C, the flask was chargedwith 140.9 grams succinic anhydride and 960 grams CARBOWAX MPEG 750 (DowChemical Company). The contents were heated to 150° C. under a nitrogensparge and esterified to a target acid value of 78, giving a monoesterintermediate with the following characteristics: Acid value=77, % Nonvolatiles=93.7; Viscosity=150 cps; Color=1 Gardner.

The flask can be cooled to room temperature and 393.7 gramstrimethylolpropane diallyl ether 90, 1.5 grams butyl stannoic acid andMIBK added to the flask. The contents may be heated to 190° C. under anitrogen sparge and esterified to an acid value less than 5 at whichpoint MIBK and excess trimethylolpropane diallyl ether 90 may be removedvia nitrogen followed by vacuum stripping. The resulting scaffoldmolecule would be designated as Scaffold Molecule D.

Scaffold Molecule E

Using the method employed for Scaffold Molecule C, the flask was chargedwith 496 grams (about 5 moles) succinic anhydride and 2,000 grams (2moles) CARBOWAX PEG 1000 (Dow Chemical Company). The contents wereheated to 150° C. under a nitrogen sparge and esterified to a targetacid value of 102, giving a diester intermediate with the followingcharacteristics: Acid value=90, % Non volatiles=99.2; Viscosity=806 cps(BROOKFIELD RVF viscometer, No. 2 spindle at 20 rpm and 35° C.); Color=1Gardner. This material was a solid at room temperature.

The flask may be cooled to near, but above, room temperature beforeadding 406.2 grams trimethylolpropane diallyl ether 90, 1.4 grams butylstannoic acid and MIBK added to the flask. The contents may be heated to190° C. under a nitrogen sparge and esterified to an acid value lessthan 5 at which point MIBK and excess trimethylolpropane diallyl ether90 may be removed via nitrogen followed by vacuum stripping. Theresulting scaffold molecule would be designated as Scaffold Molecule E.

Scaffold Molecule F

The method employed for Scaffold Molecule A was repeated using CARBOWAXpolyethylene glycol PEG 1000 (Dow Chemical Co.) in place of PEG 600glycol. Although the PEG 1000 glycol was also used to make ScaffoldMolecule E, and had approximately the same molecular weight as the triolused to make Scaffold Molecule B, a non-liquid product with aconsistency and viscosity like that of cold cream was obtained. Use ofthis product as a reactive diluent would require heating it duringcolorant, concentrate or coating composition formation, or combining itwith one or both of a very low viscosity crosslinking molecule or a verylow viscosity further scaffold molecule.

Scaffold Molecule G

Into a 4 necked, 3 liter round bottom flask was charged 480 grams (2.5moles) citric acid, 1070 grams (5 moles) of trimethylolpropane diallylether 90 (Perstorp), 2.3 grams butyl stannoic acid and MIBK. Thecontents were heated to 150° C. under a nitrogen sparge and esterifiedto a target acid value of 90. Next, 875 grams CARBOWAX MPEG 350 (DowChemical Company) were added and the flask was heated to 170° C. for twohours followed by heating to 190° C. until the acid value was <5, atwhich point MIBK was removed via nitrogen followed by vacuum stripping,giving an ethoxylated allyl diester with the following characteristics:Acid Value=1.6; % Non volatiles=96.1; Viscosity=275 cps; Color=14Gardner. The ethoxylated allyl diester was designated as ScaffoldMolecule G.

Scaffold Molecule H

Into a 4 necked, 3 liter round bottom flask was charged 1215.3 grams(6.3 moles) of citric acid, 2709.1 grams (12.7 moles) oftrimethylolpropane diallyl ether 90, 3.7 grams butyl stannoic acid and200 grams MIBK. The contents were heated to 150° C. under a nitrogensparge and esterified to a target acid value of 96 at which point MIBKwas removed via nitrogen stripping, giving a diester intermediate withthe following characteristics: Acid Value=83; % Non volatiles=98.9;Viscosity=3,150 cps; Color=1 Gardner.

The viscosity of the diester intermediate was greater than 1,000 cps,but based on the viscosity of structurally similar Scaffold Molecule G,ethoxylation should lower the viscosity of the diester intermediate. Astainless steel high-pressure reactor may be charged with theintermediate and 0.1-1% basic aqueous sodium hydroxide catalyst andheated while stirring to 130-150° C. under slight nitrogen pressure.Ethylene oxide may be fed to the reactor and allowed to polymerizesufficiently to incorporate a desired number of moles of ethylene oxideinto the intermediate. Acid may be added to terminate polymerization andthe product may be isolated via nitrogen or vacuum stripping. Theresulting scaffold molecule would be designated as Scaffold Molecule H.

Scaffold Molecule I

Into a 4 necked, 3 liter round bottom flask was charged 1152.0 grams (6moles) of trimellitic anhydride, 2568.0 grams (12 moles) oftrimethylolpropane diallyl ether 90, 3.6 grams butyl stannoic acid andMIBK. The contents were heated to 190° C. under a nitrogen sparge andesterified to a target acid value of 93 at which point MIBK was removedvia nitrogen stripping, giving a diester intermediate with the followingcharacteristics: Acid Value=74; % Non volatiles=99.4; Viscosity=8,760cps; Color=3 Gardner.

The viscosity of the diester intermediate was greater than 1,000 cps,but for the reasons discussed above in connection with Scaffold MoleculeH, ethoxylation should lower the viscosity of the diester intermediate.A stainless steel high-pressure reactor may be charged with theintermediate and 0.1-1% basic catalyst solution (e.g., aqueous sodiumhydroxide) and heated while stirring to 130-150° C. under slightnitrogen pressure. Ethylene oxide may be fed to the reactor and allowedto polymerize sufficiently to incorporate a desired number of moles ofethylene oxide into the intermediate and to reduce the viscosity of theresulting scaffold molecule. Acid may be added to terminatepolymerization and the product may be isolated via nitrogen or vacuumstripping. The scaffold molecule would be designated as ScaffoldMolecule I.

Scaffold Molecule J

Into a 4 necked, 3 liter round bottom flask was charged 1176.0 grams (12moles) of maleic anhydride and 2568.0 grams (12 moles) oftrimethylolpropane diallyl ether 90. The contents were heated to 110° C.under a nitrogen sparge and esterified to a target acid value of 180,giving a monoester intermediate with the following characteristics: AcidValue=182; % Non volatiles=88.5; Viscosity=230 cps; Color<1 Gardner.

A stainless steel high-pressure reactor may be charged with theresulting monoester intermediate and 0.1-1% basic catalyst solution(e.g., aqueous sodium hydroxide) and heated while stirring to 130-150°C. under slight nitrogen pressure. Ethylene oxide may be fed to thereactor and allowed to polymerize sufficiently to incorporate a desirednumber of moles of ethylene oxide in the resulting scaffold molecule.Acid may be added to terminate polymerization and the product may beisolated via nitrogen or vacuum stripping. The scaffold molecule wouldbe designated as Scaffold Molecule J.

Scaffold Molecule K

Into a 4 necked, 3 liter round bottom flask was charged 1078.0 grams (11moles) of maleic anhydride and 2574.0 grams (11 moles) ofpentaerythritol triallyl ether (Perstorp). The contents were heated to110° C. under a nitrogen sparge and esterified to a target acid value of169, giving a monoester intermediate with the following characteristics:Acid Value=159; % Non volatiles=84.4; Viscosity=170 cps; Color<1Gardner.

A stainless steel high-pressure reactor may be charged with theresulting monoester intermediate and 0.1-1% basic catalyst solution(e.g., aqueous sodium hydroxide) and heated while stirring to 130-150°C. under slight nitrogen pressure. Ethylene oxide may be fed to thereactor and allowed to polymerize sufficiently to incorporate a desirednumber of moles of ethylene oxide into the resulting scaffold molecule.Acid may be added to terminate polymerization and the product may beisolated via nitrogen or vacuum stripping. The scaffold molecule wouldbe designated as Scaffold Molecule K.

Scaffold Molecule L

The method employed for Scaffold Molecule B was repeated using 1 molerather than 2 moles linoleic acid. The resulting ethoxylated monoallylether had a viscosity of 193 cps and was designated as Scaffold MoleculeL.

Scaffold Molecule M

The method employed for Scaffold Molecule G was repeated using 1 moleCARBOWAX MPEG 500 (Dow Chemical Company) in place of the CARBOWAX MPEG350. The resulting ethoxylated tetraallyl ether had a viscosity of 235cps and was designated as Scaffold Molecule H.

Scaffold Molecule N

Into a 4 necked, 3 liter round bottom flask was charged 1 mole allylpentaerythritol (Perstorp), 1 mole toluene diisocyanate and 1 moleCARBOWAX MPEG 550 (Dow Chemical Company), which following reaction toconsume the isocyanate groups produced an ethoxylated triallyl ethercontaining urethane linkages and having a viscosity of 2,100 cps. Theethoxylated triallyl ether was designated as Scaffold Molecule N.

Scaffold Molecule O

The method employed for Scaffold Molecule N was repeated using 1 moleisophorone diisocyanate in place of the toluene diisocyanate, whichfollowing reaction to consume the isocyanate groups produced anethoxylated triallyl ether containing urethane linkages and having aviscosity of 1,425 cps. The ethoxylated triallyl ether was designated asScaffold Molecule O.

Scaffold Molecule P

The method employed for Scaffold Molecule N was repeated using 1 moletrimethylolpropane diallyl ether in place of the allyl pentaerythritol,which following reaction to consume the isocyanate groups produced anethoxylated diallyl ether containing urethane linkages and having aviscosity of 2,900 cps. The ethoxylated diallyl ether was designated asScaffold Molecule P.

Scaffold Molecule Q

The method employed for Scaffold Molecule O was repeated using 1 moletrimethylolpropane diallyl ether in place of the allyl pentaerythritol,which following reaction to consume the isocyanate groups produced anethoxylated diallyl ether containing urethane linkages and having aviscosity of 1,400 cps. The ethoxylated diallyl ether was designated asScaffold Molecule Q.

Example 3

Concentrates

White pigment dispersion concentrates were prepared by mixing togethervarying amounts of Crosslinking Molecule A, Scaffold Molecule B andrutile titanium dioxide particles (TIOXIDE™ TR 93 from Huntsman). Noother pigment wetting or dispersing agents or carriers were added. Theamounts of each ingredient in the white concentrates are set out belowin Table 1A.

Black pigment dispersion concentrates were prepared by mixing ScaffoldMolecule A, dioctyl maleate coalescent, various dispersants and carbonblack particles (RAVEN™ 14 from Birla Carbon), and milling 150 parts ofthe combined ingredients with 230 parts zirconia milling media until thepigment particles reached a 7.5 Hegman Grind value. The amounts of eachingredient in the black concentrates are set out below in Table 1B.

TABLE 1A White Concentrates Ingredient Run No. 3-1 Run No. 3-2Crosslinking Molecule A 22.5 20 Scaffold Molecule B 22.5 20 TiO₂particles 55.0 60 Total 100.0 100.0

TABLE 1B Black Concentrates Ingredient Run No. 3-3 Run No. 3-4 Run No.3-5 Scaffold Molecule A 40 40 40 Dioctyl Maleate 10 10 10 SOLSPERSE M387(Lubrizol) 20 DISPERBYK 2013 (Byk-Chemie) 20 DISPERBYK-145 (Byk-Chemie)20 RAVEN 14 carbon black 30 30 30 Total 100 100 100

Each concentrate formed a stable dispersion and useful factoryintermediate that could be “let down” by the addition of additionalingredients to provide colorants or coating compositions. The whiteconcentrates of Run Nos. 3-1 and 3-2 were each let down by therespective addition of 10 wt. % or 20 wt. % Crosslinking Molecule A andshaken for 3 minutes on a HARBIL™ paint shaker to provide two similardispersions containing 50 wt. % pigment solids and 100 wt. % nonvolatilematerials. The letdown compositions were slightly thixotropic liquidswith a viscosity of 74 cps. Their nonvolatilizing nature was verified byheating the letdown compositions in a pie plate for 1 hour at 110° C.whereupon less than 0.35% measured weight loss was observed. Whenevaluated according to ASTM D6886 using methyl palmitate as the boilingpoint marker, the letdown compositions exhibited less than 30 g/L VOCs.The letdown compositions also had good storage stability, as verified bystoring them for 4 days at 140° C. with no observed separation orsettling, and with full preservation of good flow properties. Theletdown compositions were combined with a metal drier package containing4.5 wt. % BORCHI Oxy-Coat 1310 metal catalyst (0.09 wt. % iron) from OMGBorchers GmbH and 1.875 wt. % NUXTRA Zirconium 24% from Huls America,Inc., drawn down on aluminum substrates as 0.08 mm (3 mil) thick opaquewhite films, left to dry at room temperature and evaluated for cureusing a five point scale in which a value of 1 represents a wet coating,2 represents a very tacky coating, 3 represents a slightly tackycoating, 4 represents a coating that is tack-free but may be indentedwith a fingernail, and 5 represents a coating that is tack-free and notindentable with a fingernail. The wet drawdown films became dry butslightly tacky at 4 days and tack free but indentable using a fingernailat 5 days. The letdown compositions accordingly provided stableone-component air-dry coating compositions.

The black concentrates of Run Nos. 3-3 through 3-5 had respectiveviscosities (as measured using a BROOKFIELD KU+ viscometer) of 140+,140+ and 129 Krebs Units (kU). They may be used to form letdowncompositions and stable one-component air-dry coating compositions likethose made from the white concentrates of Run Nos. 3-1 and 3-2.

Example 4

Clearcoats

Crosslinking Molecule A was used as is or combined with 25 wt. % or 50wt. % LARAPOL™ A 18 aldehyde resin using a high speed mixer to providethree formulations shown below in Table 2:

TABLE 2 Ingredient Run No. 4-1 Run No. 4-2 Run No. 4-3 Crosslinking 200200 200 Molecule A LARAPOL A 18 resin — 67 200 Mixing Conditions — 4hours at 4 hours at 62° C. 52° C.

The three formulations were combined with a metal drier packagecontaining 0.015% cobalt (0.125 wt. % DUROCT Cobalt 12% NX from DuraChemicals, Inc.), 0.015% manganese (0.125 wt. % OMG 12% Manganese fromOMG Borchers GmbH) and 0.15% zirconium (0.625 wt. % NUXTRA Zirconium24%), then drawn down as 0.08 mm (3 mil) thick films on aluminumsubstrates, left to dry at room temperature and evaluated to determinehow many days were required to form a tack free film that did or did notexhibit indentation when pressed with a fingernail. The hardened filmswere clear and colorless. The results are set out below in Table 3:

TABLE 3 Drawdown Results Days Until Tack-Free Days Until Run with FingerTack-Free with No. Composition Nail Indentation No Indentation 4-1 NeatReactive 13 16 Diluent 4-2 25 wt. % Resin 6 13 4-3 50 wt. % Resin 6 Notobserved in 24 days

The results in Table 3 show that the reactive liquid diluent combinedwith a metal drier package and an optional film-forming polymeric bindercould provide tack free films with good final properties.

Example 5

Reactive Diluents

Crosslinking Molecules A and B and Scaffold Molecules A and B were mixedat two different ratios to form eight different liquid reactivediluents. The viscosities for each mixture were measured an Anton PaarMCR 302 Modular Compact Rheometer with a CP50-1, 50 mm diameter 1°measuring cone at a temperature of 25° C. and a shear rate of 100/sec,and evaluated 30 seconds after the start of measurement to avoid initialoscillations in the measured viscosity values. The mixtures all hadviscosities below 1,000 cps, and exhibited Newtonian behavior whenevaluated at increasing shear rates. The reactive diluents were combinedwith the metal drier package used in Example 4. The resulting mixtureswere drawn down as 0.08 mm (3 mil) thick films, left to dry at roomtemperature and evaluated to determine how many days were required toform a tack free film that did not exhibit indentation when pressed witha fingernail. The hardened films were clear and colorless. When themetal drier package was excluded, tack free films were not obtained evenafter three weeks standing time. The results are set out below in Table4:

TABLE 4 Drawdown Results Ratio, Days Crosslinking until Run CrosslinkingScaffold Molecule:Scaffold Viscosity, Tack- No. Molecule MoleculeMolecule cps Free 5-1 A A 66:33 101 21 5-2 A A 85:15 103 4 5-3 B A 66:33208 21 5-4 B A 85:15 294 4 5-5 A B 66:33 132 21 5-6 A B 85:15 117 4 5-7B B 66:33 280 21 5-8 B B 85:15 346 4

The results in Table 4 show formation of tack-free films from lowviscosity crosslinking molecule:scaffold molecule mixtures. Thecrosslinking molecule and scaffold molecule are not required to formtack-free films, but formation of tack-free films provides good evidencethat the reactive liquid diluent will not plasticize a final curedcoating composition.

Example 6

Latex Viscosity Stability

The reactive liquid diluents of Example 5 were added at various levelsto a tintable latex base paint (VALSPAR™ SIGNATURE™ Semi-Gloss InteriorBase C No. 98824) containing the metal drier package of Example 5, andevaluated to determine initial viscosity and viscosity after standing ina sealed paint container for one day. The untinted base paint was alsoevaluated with and without the metal drier. For further comparisonpurposes, a conventional humectant/dispersant combination (CARBOWAXpolyethylene glycol PEG400 from Dow Chemical Co. and NOVEL™ 23E7ethoxylate from Sasol North America) was also added to the latex basepaint. The results are shown below in Table 5:

TABLE 5 Viscosity Stability Viscosity Wt. % Initial After AdditiveViscosity 1 Day Added Change Viscosity Change Into Initial vs. After vs.Latex Viscosity, untinted, 1 Day, untinted, Additives Base cps cps cpscps Base w/no — 133.8 — 128.2 — metal driers Base w/ As in 129.6 −4.2129.2 1.0 metal driers Example 5 PEG400/ 2.5% each 64.8 −69.0 63.4 −64.8NOVEL 23E7 Ethoxylate Run No. 5-1 in  2% 133.8 0.1 131.9 3.7 basew/metal  5% 146.9 13.2 144.8 16.7 driers 10% 217.1 83.4 197.3 69.2 RunNo. 5-2 in  2% 136.7 2.9 142.1 14.0 base w/metal  5% 149.6 15.8 152.524.4 driers 10% 207.3 73.6 200.3 72.1 Run No. 5-3 in  2% 133.8 0.0 140.011.9 base w/metal  5% 143.4 9.6 148.1 20.0 driers 10% 178.0 44.2 186.157.9 Run No. 5-4 in  2% 133.2 −0.6 138.4 10.2 base w/metal  5% 142.3 8.6148.4 20.2 driers 10% 156.7 22.9 166.9 38.8 Run No. 5-5 in  2% 122.3−11.5 126.7 −1.5 base w/metal  5% 115.6 −18.2 116.9 −11.3 driers 10%133.1 −0.6 111.1 −17.1 Run No. 5-6 in  2% 131.1 −2.7 132.6 4.4 basew/metal  5% 136.1 2.3 137.3 9.2 driers 10% 184.4 50.7 164.8 36.7 Run No.5-7 in  2% 121.5 −12.3 121.5 −6.7 base w/metal  5% 112.3 −21.5 114.6−13.6 driers 10% 107.1 −26.7 108.8 −19.4 Run No. 5-8 in  2% 131.9 −1.9131.3 3.2 base w/metal  5% 131.1 −2.7 138.2 10.0 driers 10% 136.5 2.8142.7 14.6

The results in Table 5 show that less viscosity change was exhibitedwhen using the reactive liquid diluent than when using the conventionalhumectant/dispersant combination.

Example 7

Alkyd Viscosity Stability

Using the method of Example 6, the reactive liquid diluents of Example 5were added at various levels to a tintable alkyd base paint (VALSPARANTI-RUST ARMOR™ Gloss Interior/Exterior Clear Base No. 21829) andevaluated to determine initial viscosity and viscosity after standing. Ametal drier package was already present in the base paint and thusadditional metal driers were not added. The results are shown below inTable 6:

TABLE 6 Alkyd Viscosity Stability Viscosity Initial After Viscosity 1Day Wt. % Change Viscosity Change Additive Initial vs. After vs. AddedInto Viscosity, untinted, 1 Day, untinted, Additives Alkyd Base cps cpscps cps None — 336.7 — 342.75 — PEG400/ 2.5% each 370.3 33.6 375.85 33.1NOVEL 23E7 Ethoxylate Run No.  2% 306.9 −29.8 311.7 −31.05 5-1  5% 270.9−65.8 272.75 −70 10% 223.6 −113.2 223.35 −119.4 Run No.  2% 291.3 −45.5302.5 −40.25 5-2  5% 250.7 −86.1 257.55 −85.2 10% 201.1 −135.7 210.65−132.1 Run No.  2% 306.5 −30.2 320.05 −22.7 5-3  5% 277.4 −59.4 280.85−61.9 10% 234.2 −102.5 241.25 −101.5 Run No.  2% 294.8 −41.9 313.15−29.6 5-4  5% 259.4 −77.3 269.4 −73.35 10% 220.3 −116.5 225.05 −117.7Run No.  2% 313.4 −23.3 320.05 −22.7 5-5  5% 280.9 −55.9 289.8 −52.9510% 241.7 −95.1 248.55 −94.2 Run No.  2% 295.0 −41.7 306.5 −36.25 5-6 5% 259.4 −77.3 272.1 −70.65 10% 217.8 −119.0 219.6 −123.15 Run No.  2%321.1 −15.7 327.95 −14.8 5-7  5% 291.5 −45.3 302.95 −39.8 10% 259.9−76.9 263.95 −78.8 Run No.  2% 300.7 −36.1 309.15 −33.6 5-8  5% 280.1−56.7 277.1 −65.65 10% 228.6 −108.2 237.9 −104.85

The results in Table 6 show that somewhat greater viscosity change wasexhibited in the alkyd base paint when using 5 wt. % of the reactiveliquid diluent than when using 5 wt. % of the conventionalhumectant/dispersant combination. Use of lower amounts of the reactiveliquid diluent tended to provide reduced viscosity change, and use ofgreater amounts of the reactive liquid diluent tended to provideincreased viscosity change.

Example 8

Latex Blocking Test

In a series of runs, the reactive liquid diluents and metal drierpackage of Example 5 were added to the Example 6 latex base paint andevaluated for blocking resistance according to ASTM D-4946-89, using the1-10 scale shown below in Table 7:

TABLE 7 Blocking Resistance Ratings Rating Observed Tack or AdhesionUpon Separation 10 No Tack 9 Trace Tack 8 Very Slight Tack 7 Very Slightto Slight Tack 6 Slight Tack 5 Moderate Tack 4 Very Tacky/No Seal 3  5To 25% Seal 2 25 To 50% Seal 1 50 To 75% Seal 0  75 To 100% Seal

The coatings were dried for one week at room temperature, then evaluatedfor blocking under two conditions. The first condition involved placing8.9×8.9 cm square samples in face-to-face relationship under a 500 gweight for one hour at room temperature, and the second conditioninvolved placing 8.9×8.9 cm square samples in face-to-face relationshipunder a 500 g weight for one hour in a 49° C. oven. The results areshown below in Table 8:

TABLE 8 Latex Blocking Resistance Wt. % Additive Blocking Blocking AddedInto Resistance, Resistance, Additives Latex Base 1 hour at RT 1 hour at49° C. Base w/no metal — 10 10 driers Base w/ As in 10 10 metal driersExample 5 PEG400/ 2.5% each 7 6 NOVEL 23E7 Ethoxylate Run No. 5-1 in  2%10 10 base w/metal  5% 10 10 driers 10% 9 9 Run No. 5-2 in  2% 10 10base w/metal  5% 10 10 driers 10% 9 9 Run No. 5-3 in  2% 10 10 basew/metal  5% 10 10 driers 10% 9 9 Run No. 5-4 in  2% 10 10 base w/metal 5% 10 10 driers 10% 9.5 9 Run No. 5-5 in  2% 10 10 base w/metal  5% 1010 driers 10% 9 8 Run No. 5-6 in  2% 10 10 base w/metal  5% 10 10 driers10% 9 8 Run No. 5-7 in  2% 10 10 base w/metal  5% 10 9 driers 10% 9 8Run No. 5-8 in  2% 10 10 base w/metal  5% 10 10 driers 10% 9 8

The results in Table 8 show very good blocking resistance, and asignificant improvement over the blocking resistance obtained when usingthe conventional humectant/dispersant combination.

Example 9

Alkyd Blocking Test

Using the method of Example 8, the reactive liquid diluents of Example 5were added to the Example 7 alkyd base paint and evaluated for blockingresistance. As was the case for Example 7, a metal drier package wasalready present in the base paint and thus additional metal driers werenot added. The results are shown below in Table 9:

TABLE 9 Alkyd Blocking Resistance Blocking Wt. % Additive BlockingResistance, Added Into Resistance, 1 hour at Additives Alkyd Base 1 hourat RT 49° C. None — 8 8 PEG400/NOVEL 2.5% each 7 4 23E7 Ethoxylate RunNo. 5-1  2% 9 8  5% 9 8 10% 9 7 Run No. 5-2  2% 9 9  5% 9 9 10% 9 8 RunNo. 5-3  2% 9 8  5% 9 8 10% 9 8 Run No. 5-4  2% 9 9  5% 9 9 10% 9 8 RunNo. 5-5  2% 9 8  5% 9.5 7 10% 9 5 Run No. 5-6  2% 9 8  5% 9.5 8 10% 9 7Run No. 5-7  2% 9 8  5% 9 8 10% 9 7 Run No. 5-8  2% 9 8  5% 9 8 10% 9 8

The results in Table 9 show generally very good blocking resistance, anda significant improvement over the blocking resistance obtained whenusing the conventional humectant/dispersant combination.

Example 10

LTC Improvement

Crosslinking Molecule A was combined with various latex paints and foundto reduce LTC and function as a coalescent. The LTC performance wasequal to or better than several industry standard latex paintcoalescents including dioctyl maleate, tributyl citrate, ethylene glycolmonobutyl ether and TEXANOL ester alcohol. A comparison to TEXANOL esteralcohol was for example performed by formulating four exterior 50 g/LVOC latex paints having respective binder Tg values of 6° and 44° C. forthe multistage latex binder used in Run No. 10-1, and 5°, 15°, and 22°C. for the single stage latex binders used in Run Nos. 10-2 through10-4. The paints were combined with 2.6 Kg (5.75 lbs) of TEXANOL esteralcohol per 378.5 liters (100 gallons) of paint in Run No. 10-1, or with2.6 Kg (5.75 lbs) of Crosslinking Molecule A per 378.5 liters (100gallons) of paint in Run Nos. 10-2 through 10-4. Properties for theresulting paints are shown below in Table 10:

TABLE 10 Run No. Run No. Run No. Run No. 10-1 10-2 10-3 10-4 Binder Tg6/44° C. 5° C. 15° C. 22° C. TEXANOL ester alcohol, 0.0069 Kg/liter(lb/gal) (0.0575) Crosslinking Molecule A, 0.0069 0.0069 0.0069 Kg/liter(lb/gal (0.0575) (0.0575) (0.0575) Finished Paint Density 1.05 1.04 1.051.05 Kg/liter (lb/gal) (8.74) (8.69) (8.73) (8.75) Low Temperature PassPass Pass Fail Coalescence 60° Gloss 72 70.2 72.1 70.8 60° Gloss 91 81.185.9 88.9 Scrub Resistance, 878 1806 1049 1224 ASTM D2486-06

The TEXANOL ester alcohol level in the paint of Run No. 10-1 was at arecommended addition level in order to pass the LTC test. Use of thedisclosed reactive liquid diluent in place of the conventionalcoalescent enabled passage of the LTC test using a binder having atleast a 10° C. higher minimum Tg. Although the paint of Run No. 10-4 didnot pass the LTC test at the reactive liquid diluent addition levelemployed, use of additional reactive liquid diluent should enablepassage of the LTC test. As shown in Table 10, use of the reactiveliquid diluent in the paints of Run Nos. 10-2 through 10-4 did notadversely impact gloss and scrub resistance properties compared to thepaint of Run No. 10-1.

Example 11

Acrylic Urethane Coating

Using the method of Example 5, the reactive liquid diluents of Run Nos.5-2, 5-4, 5-6 and 5-8 were added at 5 wt. % and 10 wt. % levels to 28.52g of the Part A portion of BENJAMIN MOORE™ INSL-X V500.87 COROTECH™Aliphatic Acrylic Urethane (a two-part product from Benjamin Moore & Co.supplied in Part A and Part B portions). The thus-modified Part Aportion was combined with 6.4 g of the Part B portion. No metal drierpackage was employed. No separation or other mixing anomalies werenoted. The resulting coating compositions and an unmodified sample ofthe mixed two-part acrylic urethane were drawn down as 0.10 mm (4 mil)thick films on aluminum panels. The drawdowns were allowed to cure forone week at room temperature and evaluated for appearance, methyl ethylketone (MEK) rub resistance and pencil hardness. No coating defects wereobserved in any of the cured coatings. The observed MEK and pencilhardness test results (101 double rubs and a 6H+ pencil hardness) werethe same for all compositions including both the unmodified acrylicurethane and the compositions containing the reactive diluent.

Example 12

Epoxy Coating

Using the method of Example 11, the reactive liquid diluents of Run Nos.5-2, 5-4, 5-6 and 5-8 were added at 5 wt. % and 10 wt. % levels to 15.90g of the Part A Base portion of BENJAMIN MOORE INSL-X V400.87 COROTECHPolyamide Epoxy (a two-part product from Benjamin Moore & Co. suppliedin Part A and Part B portions). The thus-modified Part A portion wascombined with 15.7 g of the Part B Converter portion. No metal drierpackage was employed. No separation or other mixing anomalies werenoted. The resulting coating compositions and an unmodified sample ofthe epoxy were drawn down as 0.08 mm (3 mil) thick films on aluminumpanels. The drawdowns were allowed to cure for one week at roomtemperature and evaluated for appearance, methyl ethyl ketone (MEK) rubresistance and pencil hardness. No coating defects were observed in anyof the cured coatings. The observed MEK and pencil hardness test results(101 double rubs and a 6H+ pencil hardness) were the same for allcompositions including both the unmodified epoxy and the compositionscontaining the reactive diluent.

Example 13

Other Coating Compositions

Using the method of Examples 6 through 12, other commercially availablecoating compositions may be modified by employing the disclosed reactiveliquid diluents in a colorant added at the point-of-sale or duringin-plant manufacture of the coating composition. Coating compositionsthat may be so modified include the BEHR™, BEHR PRO™, MARQUEE™, PREMIUMPLUS™ and PREMIUM PLUS ULTRA™ interior and exterior product lines fromBehr; the GLIDDEN™, DUO™, GRIPPER™, HIGH ENDURANCE™ PREMIUM™ and SPRED™interior and exterior product lines from Glidden; the ASSURE™, OLYMPIC™,OLYMPIC ONE™, OLYMPIC HOME™ and OLYMPIC ICON interior and exteriorproduct lines from PPG; and the INFINITY™, SHOWCASE™ and OVATION™interior and exterior product lines from Sherwin-Williams. These paintand primer systems or their associated colorants may be modified byreplacing all or a portion of the conventional coalescents or humectantsthey employ with the disclosed reactive liquid diluents. If not alreadypresent in the base paint or primer in sufficient amounts, metal driersor other catalysts like those used above may be added to facilitate thecure response of the reactive liquid diluent, and in some embodiments toalso enhance or improve the properties of the cured paint films.

Example 14

Tinted Paints

Tinted paints were prepared by combining 1 g portions of the Run No. 3-3through 3-5 black concentrates with 70 g of VALSPAR MEDALLION™ SatinInterior Pastel Base No. 3408 or with 70 g of VALSPAR ANTI-RUST ARMORInterior/Exterior Oil Based Enamel Tint Base No. 21805. The tintedsamples were shaken on a paint shaker for 3 minutes and 9 minutes,compared to determine the extent of color strength change and change inthe CIELAB color parameter ΔE*, and then evaluated for color developmentusing a standard rubup test. Minor color strength differences weremeasured when the samples shaken for 3 minutes and 9 minutes wereanalyzed using a spectrophotometer, but no visual difference wasobserved in the respective rubup samples. Set out below in Table 11 arethe color strength ratios for each tinted paint (measured as the ratioof the color strength for the sample shaken 3 minutes divided by thecolor strength for the sample shaken 9 minutes), the ΔE* value for thesample shaken 3 minutes compared to the sample shaken 9 minutes, and theappearance of the rubup samples:

TABLE 11 Tinted Paints Run No. 3-3 Run No. 3-4 Run No. 3-5 Ingredient orValue Concentrate Concentrate Concentrate Color Strength ratio, 98.97%99.38% 95.92% Latex Base ΔE*, Latex Base 0.39 0.25 1.32 Rubup ColorDevelopment Very Slight Very Slight Dark in Latex Base Light Light ColorStrength ratio, 101.48 101.04 99.22 Enamel Base ΔE*, Enamel Base 0.550.38 0.14 Rubup Color Development Very Slight Very Slight Slight Lightin Enamel Base Light Light

The results in Table 11 show that the concentrates of Run Nos. 3-3 and3-4 exhibited universal paint compatibility in latex and enamel paints,good color stability under varying shear conditions and minimal rubup.The concentrate of Run No. 3-5 exhibited good color stability undervarying shear conditions and minimal rubup in an enamel paint.

Example 15

Colorants

The concentrates of Run Nos. 3-3 to 3-5 were let down with typicalcoating composition adjuvants to form fluid colorants. The results areshown below in Tables 12 and 13:

TABLE 12 Waterborne Colorants Ingredient or Value Run No. 15-1 Run No.15-2 Run No. 15-3 Run No. 3-3 Concentrate 50   Run No. 3-4 Concentrate50   Run No. 3-5 Concentrate 50   Nonionic Surfactant  10.62  10.62 10.62 Anionic Surfactant   5.38   5.38   5.38 Anionic Surfactant   1.21  1.21   1.21 Water  35.71  35.71  35.71 Total 102.92 102.92 102.92Colorant Viscosity, (kU) 140+   140+   140+  

TABLE 13 Solvent-Borne Colorants Run No. Run No. Run No. Ingredient orValue 15-4 15-5 15-6 Run No. 3-3 Concentrate 50 Run No. 3-4 Concentrate50 Run No. 3-5 Concentrate 50 Dispersant 6.38 6.38 6.38 Dispersant 0.60.6 0.6 Cationic Polymer 0.11 0.11 0.11 Propylene Glycol 13 13 13Monomethyl Ether Acetate Total 70.09 70.09 70.09 Colorant Viscosity,(kU) 64 65 63

The Table 13 and Table 14 colorants exhibited good letdowncharacteristics. The Table 13 colorants were thick but pumpable fluids.The Table 14 colorants were fluids of lower viscosity.

Example 16

Colorant Array

A commercially-available 14 colorant array was modified by adding 10 wt.% of Crosslinking Molecule A to each colorant in the array. Thecolorants contained conventional dispersants, extenders, surfactants,defoamers and preservatives, together with pigments in the amounts shownbelow in Table 14. The modified colorants were ground using zirconiummill beads to a 7 Hegman fineness of grind value. The modified colorantviscosities were evaluated using a BROOKFIELD KU+ viscometer, and themodified colorant drying times were evaluated using the sand trail testdescribed in U.S. Pat. No. 8,822,580 B2 (Korenkiewicz et al.). Theresults are shown below in Table 14:

TABLE 14 Wt. % Viscosity Colorant Hue Pigment Pigment (KU) Sand TrailTime White PW6 55.43 115 >24 Hours Black PBK7 8.95  68 >24 Hours OrganicYellow PY74 32.26 134 >24 Hours Medium Yellow PY74 + PY83 37.14  140+ <1Hour Durable Yellow PY74 + PY184 52.14 131 <1 Hour Green PG7 19.97134 >24 Hours Blue PB15:2 14.38 121 >24 Hours Interior Red PR112 10.97 95 >24 Hours Exterior Red PR254 14.80  81 >24 Hours Magenta PR122 15.17125 >24 Hours Orange PO73 25.31  98 <1 Hour Yellow Oxide PY42 55.36 111<1 Hour Red Oxide PR101 62.39  140+ >24 Hours Raw Umber PBR7 19.91132 >24 Hours

Sand trail Times greater than 24 hours are desirable, and indicate thecolorant should not cause dispenser tip plugging in automated or manualcolorant dispensing equipment during periods when the dispenser is idle(e.g., overnight or during holidays). For the array of unmodifiedcommercial colorants on which the above formulations were based, onlythe white colorant exhibited a Sand Trail Time greater than 24 hours,with all other colorants in the array exhibiting Sand Trail Times lessthan 1 hour. The modified colorant array provided a significantreduction in potential dispenser tip plug formation in all except themedium yellow, durable yellow, yellow oxide and orange colorants. TheSand Trail Times for these latter colorants could be improved byincreasing the reactive liquid diluent content, or by including ascaffold molecule in the reactive liquid diluent. This was demonstratedfor the yellow oxide colorant by increasing its Crosslinking Molecule Alevel from 10 wt. % to 30 wt. % of the total colorant weight. Doing soincreased the Sand Trail Time to more than 24 hours. A similarmodification should provide Sand Trail Times greater than 24 hours forthe medium yellow, durable yellow and orange colorants.

Custom-tinted paints were prepared by mixing the modified colorants withpastel and clear bases using an automated colorant dispenser capable ofdispensing a 1/384 fluid ounce (0.077 cm³) minimum dispensing quantity.The modified colorants were universal colorants compatible with bothsolvent- and water-based paints and coatings.

The modified colorants could be further modified by adding the disclosedmetal drier package to each colorant. The metal drier could also orinstead be incorporated in the base paint, or dispensed from a separatedispenser canister containing the metal drier package and optionallyfurther containing a suitable prime pigment (e.g., titanium dioxide, toprovide additional hiding) or an extender pigment (e.g., talc, kaolinclay, calcium carbonate or other conventional extender). Inclusion ofthe metal drier package would assist in cured film formation and helpreinforce or enhance rather than detract from the performance of thefinal cured coating composition film.

Example 17

UV Curing Wood Coating

UV cure wood stain compositions typically employ a UV curable colorant.A wood stain formulation may be made by mixing the ingredients shownbelow in Table 15:

TABLE 15 Ingredient Amount, Parts Dipropyleneglycol Diacrylate (DPGDA)Monomer 45 SOLMER ™ SE1500 Oligomer 45 IRGACURE 369 Photoinitiator 5Pigment Dispersion containing 30 wt. % carbon 5 black in CrosslinkingMolecule B

The formulation shown in Table 15 should provide comparable appearanceand performance to a conventional stain formulation using the sameamount of a UV curable colorant such as PENN COLOR™ Black 9B1.

Example 18

Evaluation of High Viscosity Reactive Surfactants

Five commercially available E-SPERSE™ reactive surfactants for use inemulsion polymerization were obtained from Ethox Chemicals, LLC. Thereported descriptions and functionalities for these surfactants areshown below in Table 16. Their measured viscosities are also shown inTable 16. The first four listed surfactants are reported to contain 99%solids. The last listed surfactant is reported to contain only 50%solids, and if measured without its carrier should have a viscosity wellabove 1,000 cps.

TABLE 16 No. of Functional Viscosity Surfactant Description GroupsSpindle RPM cps E-SPERSE Anionic, Sulfate, One 7 20 28000 RS-1596 NH⁴⁺Salt E-SPERSE Nonionic One 5 20 5820 RS-1616 E-SPERSE Nonionic Two 5 203960 RS-1617 E-SPERSE Anionic, Sulfate, Two 7 20 33400 RS-1618 NH₄ ⁺Salt E-SPERSE Anionic, Phosphate, Two 3 20 630 RS-1684 NH₄ ⁺ Salt (50%solids)

Varying amounts of Crosslinking Molecule A, Scaffold Molecule G and theTable 16 surfactants were combined with the metal drier package (4.5 wt.% BORCHI Oxy-Coat 1310 metal catalyst and 1.875 wt. % NUXTRA Zirconium24%) used in Example 3, and mixed to provide clearcoat compositions.Drawdowns were prepared on unprimed aluminum substrates using a 16 gaugewire rod. The drawdowns were allowed to air dry and evaluated for cureover a one month period, using a five point scale in which a value of 1represents a wet coating, 2 represents a very tacky coating, 3represents a slightly tacky coating, 4 represents a coating that istack-free but may be indented with a fingernail, and 5 represents acoating that is tack-free and not indentable with a fingernail. Afterone month, several of the cured samples were evaluated for pencilhardness and for rub resistance using methyl ethyl ketone (MEK). Set outbelow in Tables 17 and 18 are the ingredients in each composition andthe observed cure results:

TABLE 17 Ingredient Run 18-1 Run 18-2 Run 18-3 Run 18-4 Run 18-5 Run18-6 Crosslinking Molecule A 16.75 16.75 16.75 16.75 16.75 16.75Scaffold Molecule G 8.25 E-SPERSE RS-1596 8.25 E-SPERSE RS-1616 8.25E-SPERSE RS-1617 8.25 E-SPERSE RS-1618 8.25 E-SPERSE RS-1684 8.25 Total25 25 25 25 25 25 Cure State At:  2 days 1 1 1 1 1 1  3 Days 3 1 1 1 1 1 6 Days 5 4 2 2 4 1  8 Days 5 4 3 3 4 2 23 Days 5 5 3 3 5 5 28 Days 5 53 3 5 5 31 Days 5 5 3 3 5 5 Pencil Hardness 6H+ 3H-4H 3H-4H 3H-4H MEKRubs 101+ 7 5 36

TABLE 18 Ingredient Run 18-7 Run 18-8 Run 18-9 Run 18-10 Run 18-11 Run18-12 Run 18-13 Crosslinking Molecule A 25 Scaffold Molecule G 25E-SPERSE RS-1596 25 E-SPERSE RS-1616 25 E-SPERSE RS-1617 25 E-SPERSERS-1618 25 E-SPERSE RS-1684 25 Total 25 25 25 25 25 25 25 Cure State At: 2 days 1 3 1 1 1 1 1  3 Days 1 4 1 1 1 1 1  6 Days 3 5 2 1 1 1 1  8Days 5 5 2 1 1 1 1 23 Days 5 5 2 1 2 2 1 28 Days 5 5 2 1 2 2 1 31 Days 55 2 1 2 2 1 Pencil Hardness 6H+ 3H-4H MEK Rubs 101+ 101+

The results in Tables 17 and 18 show that compositions containing thedisclosed reactive liquid diluent provided earlier hardened filmdevelopment and more complete cure than compositions containing only thecommercial reactive surfactants. This difference is believed to be dueto insufficient functionality, too high an equivalent weight perreactive site or excessive viscosity in the commercial reactivesurfactants.

Example 19

Functional Group Evaluation

A series of reactive liquid diluent molecular species having varyingnumbers of allyl ether functional groups were combined with a metaldrier package containing 4.5 wt. % BORCHI Oxy-Coat 1101 metal catalystand 1.875 wt. % NUXTRA Zirconium 24%, mixed to provide clearcoatcompositions, applied as drawdowns on unprimed aluminum substrates usinga 16 gauge wire rod, allowed to air dry and evaluated for cure using afive point scale in which a value of 1 represents a wet coating, 2represents a very tacky coating, 3 represents a slightly tacky coating,4 represents a coating that is tack-free but soft and easily to mar, and5 represents a coating that is a tack-free hard film resistant to morethan 100 MEK rubs. A 5 rating accordingly used more stringent criteriathan were used in Examples 3 and 18. The molecular species employed andtheir calculated molecular weight, measured viscosity and allyl etherfunctionality are shown below in Table 19 together with the observedcure ratings:

TABLE 19 Cure Rating Molecular Molecular Viscosity, Allyl Ether 3 5 7 1030 species Weight cps Functionality days days days days daysCrosslinking Molecule A 510 94 4 1 2 5 5 5 Scaffold Molecule G 907 275 42 3 4 5 5 Scaffold Molecule M 1083 235 4 2 3 4 4 4 Scaffold Molecule N991 2100 3 2 2 3 3 3 Scaffold Molecule O 1039 1425 3 2 2 2 3 3 ScaffoldMolecule P 949 2900 2 2 2 2 2 2 Scaffold Molecule Q 997 1400 2 2 2 2 2 2Scaffold Molecule A 1116 95 2 1 1 1 1 1 Scaffold Molecule L 1278 193 1 11 1 1 1

The results in Table 19 show that molecular species containing fourfunctional groups provided better cure characteristics than molecularspecies containing three or fewer functional groups. Molecular speciescontaining only three functional groups formed dry but slightly tackyfilms, and should provide a reduction in VOCs compared to cured filmscontaining a nonreactive diluent. Harder film properties may be obtainedby employing a trifunctional molecular species having a lower equivalentweight per functional group than those shown in Table 19, by adding anadditional catalyst to supplement the metal drier employed, or by addingan additional crosslinker.

Having thus described preferred embodiments of the present invention,those of skill in the art will readily appreciate that the teachingsfound herein may be applied to yet other embodiments within the scope ofthe claims hereto attached. The complete disclosure of all patents,patent documents, and publications are incorporated herein by referenceas if individually incorporated.

We claim:
 1. A fluid colorant for tinting an unpigmented or pigmentedcoating composition, the colorant containing less than a continuousfilm-forming amount of a film-forming polymeric binder, and the colorantcomprising: (i) solid pigment particles dispersed in (ii) anonvolatilizing, reactive liquid diluent having a viscosity less than1,000 cps and containing at least one molecular species having at leastthree reactive unsaturated sites and having a molar equivalent weightper reactive unsaturated site that is less than 500 grams (g), whereinthe at least one molecular species having at least three reactiveunsaturated sites comprises at least 60% by weight of the reactiveliquid diluent, and (iii) water, and wherein when the reactive liquiddiluent does not by itself stably disperse the pigment particles thenthe colorant also contains (iv) one or more pigment wetting ordispersing agents.
 2. The fluid colorant according to claim 1, whereinthe solid pigment particles comprise titanium dioxide or carbon black.3. The fluid colorant according to claim 1, wherein a molecular speciesin the reactive liquid diluent has at least four reactive unsaturatedsites.
 4. The fluid colorant according to claim 1, wherein the reactiveunsaturated sites comprise (meth)allyl ether groups, vinyl ether groupsor (meth)acrylate groups.
 5. The fluid colorant according to claim 1,wherein the reactive unsaturated sites comprise at least one conjugatedcarbon-carbon double bond.
 6. The fluid colorant according to claim 1,wherein the reactive liquid diluent has a viscosity less than 500 cpsand includes a molecular species that will by itself stably dispersepigment particles.
 7. The fluid colorant according to claim 1, whereinthe reactive liquid diluent is configured to form an interpenetratingpolymer network in a cured film-forming polymeric binder.
 8. The fluidcolorant according to claim 1, wherein the reactive liquid diluent isconfigured to crosslink with a film-forming polymeric binder.
 9. Thefluid colorant according to claim 1, wherein the reactive liquid diluentis or includes a molecular species containing at least four allyl ethergroups.
 10. The fluid colorant according to claim 1, wherein a molecularspecies in the reactive liquid diluent contains up to 15 alkyleneoxyunits.
 11. The fluid colorant according to claim 1, wherein the reactiveliquid diluent also serves as a pigment wetting or dispersing agent. 12.The fluid colorant according to claim 1, wherein a molecular species inthe reactive liquid diluent also serves as a coalescent or humectant.13. The fluid colorant according to claim 1, wherein the reactive liquiddiluent comprises a molecular species having a linear polyoxyethylenesegment joined by one or more ester linkages to one or more pendantunsaturated fatty acid residues.
 14. The fluid colorant according toclaim 1, further comprising a metal drier catalyst to catalyze reactionof reactive unsaturated sites.
 15. The fluid colorant according to claim1, wherein the fluid colorant comprises between about 1 wt. % to about50 wt. % water.
 16. The fluid colorant according to claim 1, wherein thefluid colorant comprises between about 4 vol. % to about 60 vol. % solidpigment particles.
 17. The fluid colorant according to claim 1, whereinthe fluid colorant comprises between about 5 wt. % to about 60 wt. %reactive liquid diluent.
 18. A colored latex coating compositioncomprising a film-forming latex polymer binder, water, solid pigmentparticles, and a nonvolatilizing, reactive liquid diluent having aviscosity less than 1,000 cps and containing at least one molecularspecies having at least three reactive unsaturated sites and having amolar equivalent weight per reactive unsaturated site that is less than500 grams (g), at least one molecular species in the reactive liquiddiluent containing at least one reactive unsaturated site as well as atleast one hydrophilic segment that enables such species to stablydisperse the pigment particles in the coating composition.
 19. The latexcoating composition according to claim 18, wherein the solid pigmentparticles comprise titanium dioxide or carbon black.
 20. The latexcoating composition according to claim 18, wherein a molecular speciesin the reactive liquid diluent has at least four reactive unsaturatedsites.
 21. The latex coating composition according to claim 18, whereinthe reactive unsaturated sites comprise (meth)allyl ether groups, vinylether groups or (meth)acrylate groups.
 22. The latex coating compositionaccording to claim 18, wherein the reactive unsaturated sites compriseat least one conjugated carbon-carbon double bond.
 23. The latex coatingcomposition according to claim 18, wherein the reactive liquid diluenthas a viscosity less than 500 cps and includes a molecular species thatwill by itself stably disperse pigment particles.
 24. The latex coatingcomposition according to claim 18, wherein the reactive liquid diluentis configured to form an interpenetrating polymer network in a curedfilm-forming polymeric binder.
 25. The latex coating compositionaccording to claim 18, wherein the reactive liquid diluent is configuredto crosslink with a film-forming polymeric binder.
 26. The latex coatingcomposition according to claim 18, wherein the reactive liquid diluentis or includes a molecular species containing at least four allyl ethergroups.
 27. The latex coating composition according to claim 18, whereina molecular species in the reactive liquid diluent contains up to 15alkyleneoxy units.
 28. The latex coating composition according to claim18, wherein the reactive liquid diluent also serves as a pigment wettingor dispersing agent.
 29. The latex coating composition according toclaim 18, wherein a molecular species in the reactive liquid diluentalso serves as a coalescent or humectant.
 30. The latex coatingcomposition according to claim 18, wherein the reactive liquid diluentcomprises a molecular species having a linear polyoxyethylene segmentjoined by one or more ester linkages to one or more pendant unsaturatedfatty acid residues.
 31. The latex coating composition according toclaim 18, further comprising a metal drier catalyst to catalyze reactionof reactive unsaturated sites.
 32. The latex coating compositionaccording to claim 18, wherein the latex coating composition comprisesbetween about 1 vol. % to about 40 vol. % solid pigment particles. 33.The latex coating composition according to claim 18, wherein the latexcoating composition comprises between about 1 wt. % to about 60 wt. %reactive liquid diluent.